Ignition of Ethane, Propane, and Butane in Counterflow Jets

of Cold Fuel versus Hot Air Under Variable Pressures

C. G. FOTACHE, H. WANG, and C. K. LAW*

Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544

This study investigates experimentally the nonpremixed ignition of ethane, propane, n-butane, and isobutane in
a configuration of opposed fuel versus heated air jets. For each of these fuels we explore the effects of inert
dilution, system pressure, and flow strain rate, for fuel concentrations ranging between 3100% by volume,
pressures between 0.2 and 8 atm, and strain rates of 100 600 s21. Qualitatively, these fuels share a number of
characteristics. First, flame ignition typically occurs after an interval of mild oxidation, characterized by minimal
heat release, fuel conversion, and weak light emission. The temperature extent of this regime decreases with
increasing the fuel concentration, the ambient pressure, or the flow residence time. Second, the response to
strain rate, pressure, and fuel concentration is similar for all investigated fuels, in that the ignition temperatures
monotonically decrease with increasing fuel content, decreasing flow strain, and increasing ambient pressure.
The C4 alkanes, however, exhibit three distinct p-T ignition regimes, similar to the homogeneous explosion
limits. Finally, at 1 atm, 100% fuel, and a fixed flow strain rate the ignition temperature increases in the order
of ethane , propane , n-butane , i-butane. Numerical simulation was conducted for ethane ignition using
detailed reaction kinetics and transport descriptions. The modeling results suggest that ignition for all fuels
studied at pressures below 5 atm is initiated by fuel oxidation following the high-temperature mechanism of
radical chain branching and with little contribution by low-to-intermediate temperature chemistry. 1999 by
The Combustion Institute

INTRODUCTION
Ignition represents a key process in the operation and satisfactory performance of practical
combustors. Most of the understanding gained
to date on this phenomenon is based on studies
of homogeneous systems, in which transport
effects are not taken into consideration. Hence,
the only aspects relevant to homogeneous ignition are radical-concentration growth due to
chain reactions and/or thermal feedback as a
result of exothermic reactions. The ignition
phenomena in the limit of well-mixed, spatially
homogeneous systems have been extensively
studied in closed static reactors, shock tubes,
continuous flow devices, rapid compression machines, and perfectly stirred reactors. These
studies have been well reviewed [e.g., 15].
In many realistic environments such as the
Diesel engine, however, ignition occurs in the
presence of local spatial inhomogeneities, manifested as notable gradients of temperature,
*Corresponding author. E-mail: cklaw@princeton.edu

Present address: United Technologies Research Center,

East Hartford, CT 06108.

Present address: Department of Mechanical Engineering,

University of Delaware, Newark, DE 19716.
COMBUSTION AND FLAME 117:777794 (1999)
1999 by The Combustion Institute
Published by Elsevier Science Inc.

concentration, and flow velocity. To be more

specific with the above statement, we note that
the ignition of liquid fuel droplets in a hightemperature oxidizing environment is influenced by convective-diffusive mixing of evaporating fuel with oxygen, as well as heat
conduction due to spatial temperature gradients. The existence of such gradients means that
convective-diffusive transport processes can exert significant influence on the ignition event
when their characteristic time scales become
comparable to the chemical time scales relevant
at ignition.
Our present work is a step in a larger ongoing
program aiming to understand the interaction at
ignition between chemical kinetics and the convective-diffusive transport associated with a
nonpremixed system. Extending from previous
studies [6 12] in which the ignition of hydrogen,
CO, and methane in convective-diffusive systems was thoroughly examined, the focus here is
on the ignition of C2C4 alkanes, namely
ethane, propane, n-butane, and i-butane, under
a wide envelope of the system pressure, fuel
concentration, and flow strain rate.
The importance of the selected hydrocarbons
in combustion processes cannot be overstated.
Ethane and propane are common constituents
0010-2180/99/$see front matter
PII S0010-2180(98)00134-5

778
of natural gas; butane is found in commercial
gasolines, and is the lowest alkane for which
more than a single structural isomer is possible.
Its two isomers present different knocking characteristics under conditions typically found in
spark ignition engines [13, 14], which is reflected in their respective Research Octane
Numbers of 94 (n-butane) and 102 (i-butane).
Propane and butane are the simplest hydrocarbons that show the complete spectrum of higher
hydrocarbon combustion: low temperature
chain-branching and cool flames, negative temperature coefficient (NTC), intermediate and
high temperature oxidation [13].
Finally, the kinetic mechanisms of these
C2C4 hydrocarbons are necessary building
blocks in the hierarchical structure of the mechanisms of higher hydrocarbons oxidation [15],
consequently their study is an essential step in
understanding the combustion of more complex
fuels. Given the importance of these fuels, it is
not surprising that an extensive amount of research has been directed at understanding their
combustion characteristics. Comprehensive kinetic models have been proposed to account for
homogeneous C2C4 hydrocarbon ignition in
different temperature regimes [e.g., 1521]. A
systematic, detailed study on the comparative
ignition characteristics of ethane, propane, and
butane in nonpremixed, diffusive systems, however, has not been conducted.
Our present work is a contribution in this
direction. Specifically, using the prototypical
configuration of nonpremixed jets of hot air
versus cold fuel diluent mixture in counterflow,
we have determined experimentally the ignition
temperatures for ethane, propane, n-butane,
and i-butane, and their variation with fuel dilution, system pressure, and flow strain rate. In
addition, numerical modeling using detailed kinetics and molecular transport descriptions was
performed for ethane ignition, and the experimental results are interpreted on the basis of
this numerical simulation. The ignition responses of propane and the two isomers of
butane are explored mechanistically, extending
from the knowledge gained from modeling
ethane ignition, the known mechanisms of C4hydrocarbon ignition, and the comparative
trends of the present experimental results.

C. G. FOTACHE ET AL.

Fig. 1. Schematic illustration of (a) the counterflow system

and the profiles of fuel, oxygen, and intermediate concentrations and temperature along the centerline of the counterflow of cold fuel versus hot air jets, and (b) the steadystate solution for the variation in the peak intermediate
concentration as a function of air boundary temperature.
The turning point at the end of the lower branch (mild
oxidation) represents the ignition state.

METHODOLOGY
Experimental Specifications
A detailed description of the experimental apparatus can be found in Ref. 7. Briefly, the
counterflow ignition apparatus consists of two
20 mm i.d. tubular quartz burners separated by
a 20 mm distance, which are housed in a variable pressure chamber (0.115 atm). The burners direct an electrically heated air jet downward against an upward flow of cold (300 K)
fuel/nitrogen mixture, as seen in Fig. 1a. Gas
flows are monitored using mass flow controllers
(Teledyne Hastings), and the heaters are operated by a temperature feedback controller (JKem Model 250). The fluctuation of the resulting air temperature was estimated by the
thermocouple emf readings to be 612 K once
stable heater operation was achieved.
Commercially available N2 (99.9%), C2H6
(99.5%), C3H8 (99.0%), n-C4H10 (99.5%), and
i-C4H10 (99.5%) were used without further purification for pressures below 2 atm. The highpressure experiments were conducted using
manufacturer-certified pressurized mixtures of
6% n-butane and i-butane in N2.
Ignition is achieved in this experiment by a

HYDROCARBON IGNITION IN CONVECTIVE-DIFFUSIVE SYSTEMS

slow and stepwise increase of the temperature
of the air jet until flaming condition. Thus, if we
define a characteristic system response as the
peak concentration of a representative radical
species, this response would increase as the air
boundary temperature T air is increased; following the trajectory depicted in Fig. 1b. Eventually, a turning point is achieved where the
system will transition abruptly to the upper
branch which characterizes the flaming condition. The ignition state is characterized by the
flow state just prior to the onset of the flaming
condition. The characteristic ignition temperature is measured by the T air beyond which the
flame ignition occurs. For the present convective-diffusive system, this is the only unambiguous way of defining such a characteristic ignition
temperature.
Data acquisition involves the measurement
along the stagnation streamline of the distributions of axial velocity and temperature. The gas
temperature is measured using a bare ChromelAlumel (Omega Engineering K-type) thermocouple with an average bead diameter of ;0.16
mm. The thermocouple readings are corrected
to account for radiative/convective heat transfer, with an uncertainty varying between 615
and 625 K. This error is mostly responsible for
the extent of the absolute temperature error
bars used when comparing the experimental
data with results of the numerical simulation.
The relative errors which affect the trend of the
data, however, are substantially lower, ranging
between 61 to 63 K for the flame ignition
temperatures.
The axial velocity profile u 5 u( z) is determined through laser Doppler velocimetry
(LDV). Subsequently, the LDV data is fitted
locally with polynomials to determine the maximum gradient k 5 2(du/dz) max, which quantifies the flow strain rate. To enable the comparison of results obtained at variable pressures,
we employ the pressure-weighted strain rate
5 k( p/p 0 ), where p is the pressure
defined as k
and p 0 the standard pressure of 1 atm. This
represents an adequate approximation to the
rigorous density-weighted strain rate [8].
In addition, spectroscopic experiments are
conducted to analyze the light emission from
the weakly reactive state established prior to

779

ignition using the setup described in Refs. 22

and 23.
Numerical Procedure
The numerical simulation of ethane ignition is
performed along the stagnation streamline using detailed chemical kinetics and transport
descriptions. We have also attempted to model
the ignition of C3C4 hydrocarbons using a
simplified model similar to those reported in
Refs. 24 and 25, but were unable to obtain
computational ignition under the strain rate and
pressure conditions of the current study. Simulation of C3C4 hydrocarbons using a detailed
model is computationally expensive and beyond
the scope of the present study.
The ethane/air oxidation mechanism employed in this work was taken from Hunter et al.
[26]. To understand better the mild reaction
state prior to ignition, we also investigated the
visible chemiluminescent emission above the
stagnation surface. Based on our spectroscopic
investigation, a large part of emission comes
from the excited formaldehyde. To simulate the
chemiluminescent emission, we appended the
mechanism of Ref. 26 with the following reactions, involving the formation and deactivation
of excited formaldehyde CH2O* [27],
CH3O 1 OH 3 CH2O* 1 H2O

(R283)

CH2O* 1 M 3 CH2O 1 M.

(R284)

The rate parameters of these reactions are

taken from Ref. 28. The resulting model involves 48 species and 284 reversible reactions.
In the calculations the numerical code described in Kreutz and Law [8] was employed,
which is based on the steady-state stagnation
flow code of Smooke and coworkers [29, 30].
For convenience we have used the potential
flow/boundary layer formulation of the governing equations. It is noted that previous ignition
[7] and flame [23] studies have indicated that
the flame structure and the ignition temperatures do not change appreciably when using
alternative flowfield descriptions, such as the
plug flow boundary condition.
The computational procedure involves obtaining the multiple branches of a system response S-curve [31], quantified in this work by

780
the peak concentration of a representative radical versus the boundary temperature of the
heated air (Fig. 1b). The turning point on the
lower branch of the S curve identifies the
ignition state.
To analyze the dominant ignition chemistry
we have employed in this study the Computational Singular Perturbation (CSP) method of
Lam [32, 33] and the S-curve sensitivity method
described in Kreutz and Law [34]. In the CSP
analysis, we first compute the spatial distributions of species and temperature using the
convective-diffusive ignition code. We then select initial conditions for the CSP routine corresponding to the composition and temperature
at a given spatial location, generally the peak of
a representative radical. The composition of the
explosive mode, together with the flux analysis
of the species pointed at by its radical pointers
[32], provide the information necessary to identify the dominant reactions or reaction sets
responsible for the ignition behavior.

C. G. FOTACHE ET AL.

Fig. 2. Effects of fuel concentration on ethane ignition and

5
luminosity threshold temperatures at p 5 1 atm and k
300 s21. Symbols are experimental measurements, and lines
represent calculated results. Error bars indicate the absolute
error.

Effects of Fuel Concentration

RESULTS
In most situations a state of mild reactivity is
achieved with the increase in air temperature
prior to the establishment of the vigorously
burning flame. This state is signaled by chemiluminescent glow emitted from a narrow, diskshaped region situated above the stagnation
plane, on the air side of the flow field. This
luminous zone is accompanied by little or no
measurable local temperature rise. The air
boundary temperature at which this luminosity
is first observable in a darkened environment is
hereafter referred to as the luminosity threshold
(LT) temperature, which can be determined
experimentally to an accuracy of 610 K.
When the air temperature is raised even
further from the LT temperature, the glow
intensity increases progressively until ignition of
the diffusion flame occurs. Because the chemiluminescent glow is directly related to the oxidation chemistry prior to ignition, it is likely that
the chemistry responsible for this glow is also
related to the onset of ignition. We shall report
both the LT and ignition temperatures below.

Figure 2 plots the LT and the flame ignition

temperature as functions of the fuel concentration in nitrogen, for ethane at 1 atm and a strain
rate of 300 s21. The system response to fuel
dilution displays two distinct regimes. The first
regime is characterized by a high sensitivity of
the LT and ignition temperature to fuel concentration, and occurs at low fuel concentrations,
approximately below 20% by volume. Below
;5% ethane in N2 the transition to burning
regime is no longer abrupt, and the flame itself
cannot be sustained when the air temperature is
reduced. These weak situations are considered
to be out of the ignitability range. The second
regime occurs for concentrations in excess of
;30% in the fuel jet, and is described by a
relatively constant ignition temperature. This
appears to be in contrast to the inhibitive effect
of high equivalence ratio which is observed in
shock-tube [35, 36] and spark ignition (rich
mixtures) experiments [37, 38]. Similar fuel
concentration effects were observed, however,
in our earlier studies on ignition of nonpremixed counterflowing methane/air [12]. The
reason for such an insensitivity to fuel concentration can be well understood from a previous

HYDROCARBON IGNITION IN CONVECTIVE-DIFFUSIVE SYSTEMS

Fig. 3. Experimentally determined effects of fuel concentration on propane ignition and luminosity threshold tem 5 300 s21. Error bars indicate
peratures at p 5 1 atm and k
the relative error. Lines are fits to experimental data.

study [9] of methane ignition in a convectivediffusive system, and on the basis of the current
simulation study which will be discussed later.
The same trends in the dependence of LT
and ignition temperatures on fuel concentration
in the fuel jet are found in the present work for
propane/air, n-butane/air, and i-butane/air at 1
atm, as seen in Figs. 3 and 4, respectively. In the
case of propane the transition from the concentration-sensitive regime to the insensitive regime occurs at a fuel concentration similar to
that of ethane, namely 20 to 30% of fuel in the
jet. A comparison between n-butane and ibutane reveals that the ignition temperature of
i-butane is higher than that of n-butane by
about 60 K over the entire fuel concentration
range shown in Fig. 4, although the transition
between the two regimes occurs at similar fuel
concentrations.
To conclude this section we comment briefly
on the nature of the preignition glow. We
examined emission spectra taken for flow conditions close to the flame ignition temperature.
An analysis of these spectra revealed the presence of excited formaldehyde (CH2O*) bands
characteristic of cool flame emission [39, 40]. In
addition to these, we have also identified the
characteristic 3064 peak emission from OH
and a weaker emission from CH near 4315 ,

781

Fig. 4. Experimentally determined effects of fuel concentration on n-butane and i-butane ignition and luminosity
5 300 s21.
threshold temperatures at p 5 1 atm and k
Lines are fits to experimental data.

for all four fuels investigated. Similar spectral

contributions were identified in an earlier work
on propane cool flames and preignition glows by
Gaydon and Moore [41], and in the study on
engine knock by Smith et al. [42].
Effects of Aerodynamic Strain Rate
The ignition of paraffinic hydrocarbons involves
intermediate species [15] whose lifetimes may
be comparable to the characteristic time scales
of mass and heat transport [43]. Thus, transport
effects are expected to exert a significant influence on the ignition event. To quantify this
influence we have determined the response of
ignition temperatures to changes in the flow
strain rate. In our counterflow configuration the
reciprocal of the strain rate is a direct measure
of the convective residence time.
Figure 5 presents the experimentally measured LT and ignition temperature as a function
of strain rate for 6% ethane in the fuel jet and
1 atm pressure. It is seen that increasing the
flow strain rate uniformly raises the air temperature required for flame ignition. Here, an
increase in the strain rate by a factor of 4
elevates the ignition temperature by about 60 K.
The LT temperature, however, is less affected
by the strain rate, and remains nearly constant,
as seen in Fig. 5.

782

Fig. 5. Ethane ignition and luminosity threshold temperatures versus flow strain rate at p 5 1 atm, 6% C2H6 in the
fuel jet. Symbols are experimental data, and lines represent
calculated results. The error bars indicate the relative error.

Figures 6 8 present respectively the variations of the ignition temperature with respect to
strain rate for propane, n-butane, and i-butane.
It is seen that these fuels exhibit similar response to flow straining as just discussed for
ethane. The sensitivities to strain appear to be
comparable in magnitude among the four hy-

Fig. 6. Propane ignition and luminosity threshold temperatures versus flow strain rate at p 5 1 atm, 6% C3H8 in the
fuel jet. Symbols are experimental data, and lines are fits to
experimental data.

C. G. FOTACHE ET AL.

Fig. 7. n-Butane ignition and luminosity threshold temperatures versus flow strain rate at p 5 1 atm, 5% n-C4H10 in
the fuel jet. Symbols are experimental data, and lines are fits
to experimental data. The error bars indicate the relative
error.

drocarbons. In general, an increase in the strain

rate by a factor of 4 requires the air temperature
to rise by 40 60 K to achieve flame ignition.
Moreover, the effects of strain rate and fuel
concentration on ignition do not seem to be

Fig. 8. i-Butane ignition and luminosity threshold temperatures versus flow strain rate at p 5 1 atm, 5% i-C4H10 in
the fuel jet. Symbols are experimental data, and lines are fits
to experimental data. The error bars indicate the relative
error.

HYDROCARBON IGNITION IN CONVECTIVE-DIFFUSIVE SYSTEMS

783

versely, performing the fuel concentration experiments described in Figs. 2 4 at higher strain
rates would only shift the data upward in the
ignition temperature concentration curve,
without modifying the trend.
A second similarity among the four fuels is
the relative insensitivity of the LT temperature
to strain rate variation. An exception appears to
be propane, for which it would be hard to
discount the change in LT temperatures seen in
Fig. 6.
Effects of Pressure

Fig. 9. n-Butane ignition temperatures versus flow strain

rate at p 5 1 atm and different fuel concentrations in the
fuel jet. Symbols are experimental data, and lines are fits to
experimental data.

strongly coupled. As demonstrated respectively

in Figs. 9 and 10 for n-butane and i-butane
ignition at 1 atm, changing the fuel concentration by a factor of 5, i.e., from 3 to 15% in the
fuel jet, merely shifts the ignition temperatureversus-strain rate curves upward, but does not
affect the qualitative trend significantly. Con-

Fig. 10. i-Butane ignition temperatures versus flow strain

rate at p 5 1 atm and different fuel concentrations in the
fuel jet. Symbols are experimental data, and lines are fits to
experimental data.

An increase in the system pressure is generally

believed to facilitate ignition, as surmised from
the simple thermal explosion theory of Semenov
[44] for reactions with positive overall pressure
exponent. In reality, however, hydrocarbon ignition presents more complex responses in different pressure ranges, such as the cool flame
phenomena, NTC regimes, and multiple-staged
and oscillatory ignition [13, 45]. This variability
with pressure implies that conclusions derived
from atmospheric pressure studies cannot be
simply extrapolated to higher or lower pressures. Recognizing, therefore, that a truly systematic study of ignition must encompass an
extended range of the system pressures, we
expand in this section our investigation of
C2C4 nonpremixed ignition to study the effects
of pressure variation between 0.2 and 8.0 atm.
Figure 11 plots the experimentally determined ignition and LT temperatures of 6%
ethane in N2 as a function of pressure, for a
constant pressure-weighted strain rate of 300
s21. The data in Fig. 11 shows that both the LT
and the ignition temperature decrease when the
system pressure is raised. The same overall
dependence on system pressure can be observed
with the other hydrocarbons studied, as will be
seen shortly. This dependence is expected, considering that the rate-limiting processes for radical growth are typically second-order, and
therefore depend on the square of the reactant
pressure. To a first approximation, the balancing diffusive losses remain constant with pressure variation, because of the near-constancy of
the density-weighted diffusivities, hence the
need for a higher air temperature when pressure is reduced.

784

Fig. 11. Effects of pressure on ethane ignition and luminos 5 300 s21 and 6% C2H6 in
ity threshold temperatures at k
the fuel jet. Symbols are experimental measurements, and
lines represent calculated results.

An additional observation which appears to

be valid for all four hydrocarbons may be inferred. As pressure is increased, the temperature domain of the glow regime diminishes, as
seen in Fig. 11 by the gradual closure of the LT
and ignition temperature. In particular, at pressures higher than 5 atm, no glow is detected
experimentally before flame ignition and the LT
temperature curve merges with that of the ignition temperature.
Propane has a similar ignition response to
pressure as that observed with ethane. This is
seen in Fig. 12 in the variation of the experimental LT and ignition temperature with pressure determined for 6% propane in N2 and a
constant pressure-weighted strain rate of 300
s21. A somewhat higher sensitivity to pressure
increase is observed in the range of high pressures.
Finally, Figs. 13 and 14 plot respectively the
pressure dependence of the experimentally determined ignition temperature of n-C4H10 and
i-C4H10, for 5% fuel in N2 and a constant
pressure-weighted strain rate of 300 s21. It is
seen that C4 nonpremixed ignition is characterized by three distinct regimes, although the
overall dependence remains one of facilitating
ignition upon pressure increase. Under all con-

C. G. FOTACHE ET AL.

Fig. 12. Effects of pressure on propane ignition and lumi 5 300 s21 and 6% C3H8
nosity threshold temperatures at k
in the fuel jet. Symbols are experimental measurements, and
lines are fits to experimental data.

ditions, n-butane ignites more readily than ibutane.

It is seen that regime I occurs at low to
intermediate pressures, below ;5 atm, and is
similar to that encountered with ethane and
propane, namely a similar qualitative dependence of ignition temperature on pressure and

Fig. 13. Effects of pressure on n-butane ignition and lumi 5 300 s21 and 5%
nosity threshold temperatures at k
n-C4H10 in the fuel jet. Symbols are experimental measurements, and lines are fits to experimental data.

HYDROCARBON IGNITION IN CONVECTIVE-DIFFUSIVE SYSTEMS

Fig. 14. Effects of pressure on i-butane ignition and lumi 5 300 s21 and 5%
nosity threshold temperatures at k
i-C4H10 in the fuel jet. Symbols are experimental measurements, and lines are fits to experimental data.

flame ignition preceded by glow. Regime II

occurs around 5 atm and is characterized by a
rapid decrease of the ignition temperature with
even small pressure increases. This regime,
manifested as a plateau in Figs. 13 and 14,
appears similar to the behavior observed in
autoignition studies of n-butane/air mixtures
[46], where it is attributed to a transition in the
dominant chemistry to a low temperature mechanism. Regime III is characteristic of high pressures, in excess of ;6 atm, and shows an
insensitivity of the ignition temperature to pressure variation. In this regime, the ignition temperatures of n-butane and i-butane are respectively ;900 and 1010 K, and flame ignition is no
longer preceded by glow.
If the transition of P-T behavior to regimes II
and III can be attributed to a transition in the
dominant chemistry to the low-temperature or
NTC regime, we expect that propane should
also exhibit such a p-T behavior. This is because
propane also exhibits NTC behavior. Indeed,
the p-T ignition curve of propane of Fig. 12
levels off more significantly than that of ethane
in Fig. 11, when the pressure is higher than 4 to
5 atm. Hence, the p-T curve of propane may
enter into regime II or even regime III, if the
pressure is further elevated from the upper limit
of p approximately equal to 7 atm. Clearly,

785

Fig. 15. Axial temperature and species concentration profiles as a function of the distance from the fuel-jet nozzle
5 300
prior to flame ignition computed for p 5 1 atm, k
s21, 6% C2H6 in the fuel jet.

more experiments are needed to resolve this

issue.
Numerical Simulation of Ethane Ignition
To understand the convective/diffusive effects
and the chemical processes responsible for
flame ignition, we present the results of numerical modeling of ethane ignition in this section.
The simulation was performed under conditions
identical to those of the experiments described
earlier.
A typical numerical solution is shown in Fig.
15, which plots the axial distributions of major
species, temperature, and five relevant intermediates (H, HO2, CH2O, C2H5, and C2H5O2) for
a situation just prior to flame ignition, at 6%
ethane in N2, 300 s21 strain rate, atmospheric
pressure, and T air 5 1276 K. The selection of
the intermediate species is based on the consideration that while the H atom is characteristic of
high-temperature ignition mechanism dominated by
H 1 O2 3 O 1 OH

(38)

chain branching [47], the HO2 and C2H5O2 are

relevant to low-to-intermediate temperature hy-

786

Fig. 16. System response curves: peak (a) H and (b) HO2
5 300 s21, 6%
concentrations computed for p 5 1 atm, k
C2H6 in the fuel jet. Solid line: the base case calculation;
dashed lines: computations without chemical heat release.

drocarbon ignition dominated by the peroxide

chemistry.
We note that the response of the peak radical
concentration at flame ignition is similar among
all radicals, and is characterized by the turning
of the response curve as a function of a system
parameter, like the air temperature. Figure 16
plots two representative response curves, for the
peak concentrations of H and HO2 as a function
of air temperature. The computational flame
ignition is determined from such a plot as the
turning point of the response curves at ;1270
K, above which the steady-state solution, e.g.,
the H-atom concentration, can exist only on the
upper branch of the S-curve of vigorous burning. We have verified previously [9] that the
ignition temperatures achieved by this procedure are nearly identical to those obtained using
continuation algorithms which trace the response through the turning point [48]. In addition, the critical turning points are obtained at
the same air temperatures, as expected from the
steady-state nature of the analysis [9]. Indeed, it
is seen that both H and HO2 curves turn at the
same temperature, as such the ignition state can
be defined by examining the response of any

C. G. FOTACHE ET AL.
radical with respect to air temperature. Here we
choose the H atom as a representative species
for the ignition temperature identification.
The computed ignition temperature is compared with the experimental data for ethane in
Figs. 2, 5, and 11. The smooth curves in Fig. 2
are generated through 10 computational cases.
It is seen that the numerical simulation reproduces qualitatively the dependence of the ignition temperature on the fuel concentration (Fig.
2), the strain rate (Fig. 5), and the pressure (Fig.
11). In particular, the transition in the ignition
temperature response to fuel concentration is
well simulated by the numerical model, as seen
in Fig. 2. The calculated ignition temperatures
are, however, uniformly higher than the experimental values by less than 100 K. This difference is not substantial considering the uncertainties in both reaction kinetics and in the
transport coefficients.
Figure 16 also shows multiple stages of radical growth at the temperature below the ignition
point. First, when the air temperature is gradually raised up to ;1050 K, the peak concentration of the H atom grows at a nearly uniform
rate E 5 dln[H] max/d(21/RT air) of about 52
kcal/mole. This slope is comparable to the activation energy E a of the initiation step,
C2H6 1 O2 3 C2H5 1 HO2,

(R222)

which has E a 5 51 kcal/mole, and is found to

dominate the system response in this range of
temperatures of diminished reaction activities.
Around 1100 K for the situation shown in Fig.
16, an abrupt acceleration of the radical growth
ensues. Subsequently, the system enters a stage
of mild reactivity, characterized by small heat
release and partial fuel conversion. Some intermediates, such as CH2O or HO2, are formed in
amounts larger than those on the vigorous
flaming branch, as seen in Fig. 16b for HO2. The
existence of large amounts of such radical species in the mild oxidation region is likely to
correspond to the chemiluminescent glow observed experimentally.
It should be recognized, however, that the
signal at the very onset of mild oxidation may be
too weak to be visually detectable. Indeed, when
we plot the computational inflection temperature identified in Fig. 16a and compare it with

HYDROCARBON IGNITION IN CONVECTIVE-DIFFUSIVE SYSTEMS

the experimental LT temperature, we found
that the inflection temperature is significantly
lower than the experimental detection of the
glow, although the response is similar to
changes in the fuel concentration (Fig. 2), strain
rate (Fig. 5), and pressure (Fig. 11).
An alternate possibility of modeling the LT is
to assign a threshold of detection, for example,
in terms of the excited formaldehyde concentration, and subsequently monitor the air temperatures required to achieve this threshold. At 1
atm, 6% ethane in N2, and a flow strain rate of
300 s21, the experimental LT was found to be
;1170 K. The corresponding computed CH2O*
concentration is 1.5 3 10218 mol/cc. If we use
this threshold concentration as the calibration
point and define the air temperature required to
achieve this threshold as the computational LT
temperature, we found that we can model the
LT fairly well, as seen in Figs. 2 and 5 by
comparing the dashed lines with the experimental data (circles).
The computed response of LT temperature
and inflection point responses to pressure are
plotted in Fig. 11. It is seen that the inflection
point disappears at p 5 5 atm, that is, no abrupt
transition occurs between the initiation-dominated and mild oxidation regimes. In addition,
the preset threshold for CH2O* is reached near
the ignition point, or not at all for pressures in
excess of ;6 atm, in agreement with the visual
observation of the onset of glow. For this reason, the computed LT and ignition temperature
curves merge at ;6 atm.
DISCUSSION
Mechanism of Flame Ignition at Atmospheric
and Subatmospheric Pressures
We begin discussion by noting that the air
boundary temperature at ignition defined in the
Methodology section is not necessarily the temperature corresponding to that experienced by
chemical reactions responsible for flame ignition. First, the fuelair mixing region of the
counterflow system is a region where a significant temperature gradient exists (Fig. 15). Second, the heat release associated with mild oxidation prior to ignition often causes a small rise

787

in temperature above the air temperature, as is

seen in Fig. 15. Nonetheless, we note that the
more physically appropriate local temperatures corresponding to the peak of the H atom,
or to the maximum temperature in the flow, are
actually very close in value to the boundary
temperature (within 520 K). It follows that the
ignition response is virtually identical when using any of these three representations. The air
boundary temperature quantifies a global response, which is appropriate when comparing
the ignitability of different fuels. In addition,
this selection greatly facilitates the comparison
between experimental and modeling results.
The consequence of spatial concentration
and temperature gradients is that the knowledge previously learned in homogeneous ignition system is valuable but may not be directly
applicable to the current nonhomogeneous ignition system. In particular, the present situation cannot be simply understood by considering radical growth and destruction following a
reaction time, because the latter cannot be
unambiguously defined in the present diffusive
system.
In an earlier study on hydrogen/air ignition
[8] it was found that the active radicals peaked
nearly at the same spatial location, which suggested the concept of an ignition kernel of
essentially premixed nature. This concept further led to understanding the effects of changes
in external parameters such as the flow strain
rate. The intermediate species profiles in Fig. 15
show the existence of a spatially narrow reaction
zone, encompassing both the peroxide and Hatom dominated reaction chemistries which occur at different spatial locations within the
narrow reaction zone. For consistency, we shall
still call the reactive region of the counterflow
system as the ignition kernel, which develops as
a result of fuel and oxidizer mixing.
The ignition kernel extends mainly on the
oxidizer side of the stagnation plane, as exemplified by the peak concentration location of
C2H5 relative to the stagnation surface. This is
reasonable considering that the general Arrhenius dependence of reaction rates favors a
higher temperature environment at the expense
of decreasing fuel concentration. Consequently,
significant reactions occur by-and-large with an
effectively fuel-lean stoichiometry. Because the

788
reaction zone is on the oxidizer side of the
stagnation surface, the fuel must come from
convective/diffusive transport across the stagnation surface.
For ethane ignition, Fig. 15 shows that a clear
separation exists between the peaks of the
C2H5O2 and H concentrations, whereas the
HO2 profile is more broadly distributed across
the reaction zone. In general, three types of
intermediates are found: (a) the high-temperature, highly reactive radicals, like the H atom,
whose short lifetimes translate into narrowly
peaked concentration profiles situated close to
the oxidizer boundary; (b) the peroxide species,
such as C2H5O2, which are preferentially
formed at lower temperatures, and thus closer
to the fuel side; and (c) the relatively stable
species, such as CH2O and HO2, which situate
between the high-temperature radicals and the
low-temperature peroxides, and exhibit broader
distribution profiles because they are more
likely to be transported out of the reaction zone
and remain unreacted. The coexistence of all
three types of species suggests that in the
present convective/diffusive system the fuel can
be oxidized via a complete spectrum of the
high-, intermediate-, and low-temperature reaction chemistries of hydrocarbon fuels. These
chemistries are: (a) reaction kinetics dominated
by the H atoms at the high-temperature, (b)
that in the intermediate temperature range with
the HO2 as a key radical, and (c) the lowtemperature chemistry of peroxide reactions, as
exemplified by C2H5O2 and C2H5O2H.
Two related questions follow immediately
from the above discussion. First, is flame ignition a consequence of the peroxide chemistry,
or the H-atom dominated high-temperature kinetics? Second, does peroxide chemistry precondition the high-temperature kinetics? We
shall address these questions below by means of
sensitivity analyses.
Figure 17 presents a computational sensitivity
test, where the peak H-atom concentrations are
plotted as a function of the air temperature for
the case of 6% ethane in N2, 1 atm pressure, and
300 s21 strain rate. These conditions are the
same as those sample calculations shown in
Figs. 15 and 16. It is seen that removing the
representative peroxide reactions

C. G. FOTACHE ET AL.

Fig. 17. Effect of removing key elementary steps from the

kinetic model on the variation of the H-atom response curve
as a function of the air temperature. The conditions are the
same as those in Fig. 15.

C2H5O2H 3 C2H5O 1 OH

(R229)

C 2H 5 1 O 2 3 C 2H 5O 2

(R214)

from the simulation does not cause any appreciable effects on flame ignition, i.e., the temperature at the turning point remains essentially
the same. Yet removing the high-temperature
chain branching reaction
H 1 O2 3 OH 1 O

(R38)

causes the disappearance of the turning point,

or flame ignition. In addition, removing the
reaction
C2H5(1M) 3 C2H4 1 H(1M)

(R74)

causes the disappearance of the inflection point

prior to ignition, forces the growth of radical
species to require higher air temperatures, and
thus causes a higher ignition temperature as
compared to the base case.
These sensitivity analyses suggest that flame
ignition in this case is caused by the hightemperature reaction mechanism dominated by
the chain-branching reaction (R38), and the
low-temperature, peroxide chemistry is unimportant. The low-temperature chemistry appears to affect the concentration of the H-atom,
but it does not affect the ignition temperature.

HYDROCARBON IGNITION IN CONVECTIVE-DIFFUSIVE SYSTEMS

This is in direct contrast to the general understanding of the homogeneous ignition system, in
which both low- and intermediate-temperature
chemistry is known to affect the ignition behavior [49] by preconditioning the high-temperature ignition.
An important distinction between the present
diffusive configuration and the homogeneous
systems is the following. In a homogeneous
system, when temperature is increased at a
constant pressure the cool flames initiated by
the low temperature oxidation will be extinguished by the inherent transition into the NTC
regime. In our system the NTC behavior will
manifest itself at most in a slowdown of the
increase of reactivity with increasing air temperature. This is because the nonpremixed system
offers considerably more freedom. When the
temperature becomes too high, the low-temperature mechanism can simply adjust its position
closer to the cold fuel side. Consequently, we do
not observe in our nonpremixed system the
sequence ignition extinctionignition which
translates into the well-known ignition peninsula of the hydrocarbon explosion limits [50].
Because of the presence of mild oxidation
and heat release prior to ignition, the ignition
event may also be affected by chemical heat
release feedback prior to ignition. To investigate this possibility, a numerical experiment is
performed, in which the heat release is turned
off in the energy conservation equation. The
results, plotted with dashed lines in Fig. 16,
indicate that while the onset of mild oxidation
may be resolved accurately without heat release,
the flame ignition is no longer realized without
thermal feedback. This result indicates that
flame ignition occurs primarily as a combination
of high-temperature kinetics and heat release
feedback, whereas the mild oxidation regime is
entirely kinetically driven.
The above analyses should be applicable to
ethane ignition in general at pressures below 1
atm where the peroxide chemistry is less important as compared to the case at 1 atm shown in
Figs. 15 through 17, because the air temperature
at ignition is higher for p , 1 atm than that at
1 atm (Fig. 16). The analysis may be equally
applicable at elevated pressure, based on the
consideration that the pressure-versus-temperature response curve of Fig. 16 does not expe-

789

rience qualitative change over the range of

experimental conditions. Based on the same
consideration, one may further speculate that
the high-temperature chemistry causes ignition
for propane over the entire pressure range
shown in Fig. 12, and for n-butane and i-butane
ignition in regime I (high-temperature and lowpressure) of Figs. 13 and 14. Because of the
uncertainties associated with the reaction kinetics of peroxides and the transport properties of
the peroxide species, discussion of a conclusive
nature regarding the mechanism of ignition for
butane in regimes II and III can only be conducted in future modeling studies.
It is interesting to note that the occurrence of
kinetically dominated transition followed by
thermokinetic ignition has been identified for
fuels previously investigated in our convectivediffusive system, namely H2, CO/H2, CH4, and
CH4/H2. Moreover, the kinetically driven inflection point may become an actual turning point
[9, 12] within certain ranges of the strain rate,
pressure, and fuel concentration, suggesting the
possibility of double-staged ignition in the sense
of two abrupt transitions to higher states of
reactivity.
Further Examination of Reaction Kinetics
In this section, we further examine the dominant reaction kinetics of flame ignition and mild
oxidation regimes. To analyze the first acceleration of the radical concentration growth in the
system response, we have performed CSP analyses for the peaks of the ethyl peroxy C2H5O2
and H radical distributions for the case of 6%
ethane previously discussed, at the air boundary
temperature corresponding to the inflection
point (1102.5 K) of the S-curve.
The composition of the explosive mode at the
peak of the C2H5O2 radical reveals that a
mechanism of low and intermediate temperature is responsible for the C2H5O2 radical
growth at the spatial location where the temperature is approximately 400 K below the boundary air temperature. The attack on fuel occurs
mostly through
C2H6 1 HO2 3 C2H5 1 H2O2

(R221)

C2H6 1 OH 3 C2H5 1 H2O.

(R113)

790

C. G. FOTACHE ET AL.

Subsequently, the ethyl radical undergoes oxidation through the competing routes:
C2H5 1 O2 3 C2H4 1 HO2

(R213)

C 2H 5 1 O 2 C 2H 5O 2

(R214)

The C2H5O2 radical produced in R214 may (a)

internally isomerize to form C2H5O2H
C 2H 5O 2 3 C 2H 4O 2H

(R236)

which then dissociates through

C2H4O2H 3 C2H4O 1 OH

(R237)

or (b) abstract an H atom to form ethylhydroperoxide C2H5O2H which then provides

branching through homolytic fission of the OO
bond:
C2H5O2H 3 C2H5O 1 OH.

(R229)

The competing conjugate alkene route R213

is favored at slightly higher temperatures, when
the equilibrium in R214 shifts to the reactants
because of the higher activation energy of the
reverse reaction. This thermal switch mechanism is conventionally considered to be responsible for the onset of the NTC regime [51, 52] in
higher hydrocarbons, although more recently
Wilk et al. [53] have proposed an alternative
criterion for n-butane transition to NTC.
The CSP analysis at the peak of the C2H5O2
concentration shows the increased importance
of the HO2 chemistry through the reactions:
CH3 1 HO2 3 CH3O 1 OH

(R119)

C2H5 1 HO2 3 C2H5O 1 OH

(R212)

C2H5O2 1 HO2 3 C2H5O2H 1 O2.

(R232)

Additional branching comes about from the

decomposition of the hydrogen peroxide H2O2
H2O2(1M) 3 OH 1 OH,

(R-85)

with H2O2 produced primarily by R221 and

HO2 1 HO2 3 O2 1 H2O2. The reaction R-85,
characteristic of the intermediate temperature
mechanism, is highly temperature-sensitive and
hence peaks farther upstream, closer to the hot
air boundary. The main branching process at
the peak of C2H5O2 remains reaction R229,
which is representative of the low-temperature
chemistry.

At the upstream peak of the H-atom concentration, however, the CSP analysis indicates that
reactions characteristic of the intermediate- and
high-temperature mechanisms become active.
The explosive mode is dominated by the thermal decomposition of ethyl:
C2H5(1M) 3 C2H4 1 H(1M)

(R-74)

and the propagation route R213. Features of

the low-to-intermediate mechanism are still
present through the influence of R214. However, the combination of high temperature and
H production through R-74 results in activating
the branching reaction (R38), which is crucial in
flame ignition as discussed previously.
Further evidence supporting the above discussion is that the removal of R214, the source
of low-temperature oxidation, from the numerical simulation actually promotes ignition. It is
seen in Fig. 17 that the rise of the H atom
concentrations occurs at lower temperatures
and the ignition temperature is slightly lower
than the base case calculation in which R214 is
included. This result can only be interpreted by
the fact that R214 and thus the low-temperature
oxidation competes for the C2H5 radical, which
is critically needed to initiate flame ignition via
ethyl decomposition to form the H atoms. The
overall effect of fuel scavenging by low-temperature chemistry is, however, not very significant.
The removal of the low-temperature pathways
from the mechanism affects only minimally the
ignition temperature.
In addition to the CSP analysis, we also
performed an S-curve sensitivity analysis [34].
The sensitivity coefficients normalized to their
largest value are plotted in Fig. 18. A positive
sensitivity coefficient means that the reaction
promotes flame ignition, whereas a negative
sensitivity signifies that the reaction retards
ignition. The sensitivity results indicate that it is
the high-temperature reactions which have the
most significant influence in radical growth just
prior to ignition, namely the ethyl thermal decomposition R-74, the branching reaction R38,
the oxidation of CH3 by HO2 R119, and among
others,
CO 1 OH 3 CO2 1 H
HCO 1 M 3 H 1 CO 1 M.

(R99)
(R166)

HYDROCARBON IGNITION IN CONVECTIVE-DIFFUSIVE SYSTEMS

791

Effects of Transport Processes, Fuel

Concentration, and Fuel Structure

Fig. 18. S-curve sensitivity analysis under the same conditions as in Fig. 15.

The destruction of the radicals is sensitive to the

reactions
OH 1 HO2 3 H2O 1 O2

(R87)

HCO 1 O2 3 HO2 1 CO.

(R167)

Thus the sensitivity analysis further supports the

conclusion that ethane ignition at 1 atm pressure is caused mainly by the high-temperature
chain branching mechanism. Figure 18 also
shows that the oxidation of C2H5 by O2 (R213)
has a negative effect on ignition, because it
competes against R-74. In addition, the internal
isomerization of C2H5O2 to C2H4O2H also
shows a negative sensitivity coefficient, again
indicating that the low-temperature chemistry
inhibits, albeit mildly, the flame ignition. These
results are consistent with the CSP analysis.
In summary, the following interpretation of
the ignition response can be reached. When the
air temperature is low, initiation reaction R222
provides a stable, if small, pool of ethyl and
hydroperoxy radicals. As the temperature is
raised, this pool increases sufficiently such that
ethyl decomposition begins to supply sufficient
H radicals to trigger the high-temperature
branching reaction R38. This explains the first
acceleration of the system response. The lowtemperature mechanism of peroxide is also initiated. This mechanism contributes to the increase in concentration of the peroxide species,
but it does not contribute significantly to the
production of the H atom concentration, whose
growth ultimately controls the flame ignition.

The responses of the ignition temperature to

strain rate shown in Figs. 510 point to the fact
that species transport indeed affects the ignition
processes. The strain-rate dependence has been
attributed [8, 9] to a decrease in the available
residence time within the ignition kernel. The
convective residence time is inversely proportional to the flow strain rate in the counterflow
configuration [54], therefore decreases upon
increasing strain. Likewise, the ignition kernel
width varies inversely with the square root of
the strain rate [8], hence the rate of radical loss
through diffusive transport out of the kernel
also increases with increased flow straining. In
addition, the fuel must diffuse across the stagnation surface and be transported against the
convective flow of the oxidizer stream to initiate
reaction. The numerical modeling results for
ethane further support this explanation. When
strain rate is increased the reaction zone width
is reduced, and the species concentration gradients increase, resulting in enhanced rates of
diffusive loss. The computed results agree qualitatively with those obtained experimentally
(Fig. 5), even though the flame ignition temperatures remain substantially overpredicted.
The characteristic dependence of the ignition
temperature on fuel concentration (Figs. 2 4)
appears intuitively correct in that at low fuel
concentrations a fuel deficit would result in a
state of low reactivity, and hence the need for
higher ignition temperature. At high fuel concentrations the rate of reaction processes becomes limited by fuel diffusion to the ignition
kernel. The diffusionally limited supply of fuel
results in a fuel-lean stoichiometry even at
100% fuel in the jet [9]. The result is that
increasing the fuel concentration does not succeed in raising or reducing the required ignition
temperature.
The relatively constant ignition temperature
attained at large fuel concentrations allows us to
compare in a systematic fashion the ignitability
characteristics of the four paraffins. In order to
do this we define a nonpremixed ignition
temperature as the ignition temperature in the
limit of high fuel concentration (100%), for a
fixed characteristic flow strain rate and system

792

Fig. 19. Comparison among (a) shock-tube [55], (b) counterflow nonpremixed ignition (this work), and (c) autoignition [56] temperatures as a function of the hydrocarbon
chain length.

pressure. Figure 19b plots the variation of these

nonpremixed ignition temperatures as a function of the number of carbon atoms in the fuel
molecule. The ignition temperatures for n-butane and i-butane were estimated by extrapolation of least-square polynomial curve fits
through the data in Fig. 4.
It is seen that the ignition temperature initially decreases from methane to ethane, then
increases from ethane to propane, and to butane. This could be a manifestation of the
differences in reaction kinetics, as well as the
influence of decreasing mass diffusivity which
accompanies the transition to larger hydrocarbons. The lower fuel diffusivity implies a position of the reaction zone closer to the stagnation
plane, thereby occurring at lower temperatures.
As a result, the boundary temperature must
increase for ignition to occur. Moreover, numerical simulations performed for ethane ignition appear to support this explanation. Specifically, our calculations show that the ignition
temperature can increase by 30 40 K if the
diffusivity of ethane is artificially decreased to
that of butane. While this increase may not be
sufficient to modify the ranking in Fig. 19b, it
does substantiate the importance of fuel diffusivity in effecting ignition.

C. G. FOTACHE ET AL.
We must note, however, that the trend in Fig.
19b is not determined entirely by the diffusive
properties of the fuel. Ignition is a result of
complex interactions between chemical kinetics
and transport phenomena. An example is the
ignition of methane [9]. As seen in Fig. 19b,
methane remains the most difficult hydrocarbon
to ignite, its higher diffusivity notwithstanding.
In addition, the two isomers of butane have
similar transport properties, however, i-butane
is more difficult to ignite than its straight-chain
counterpart as seen in Fig. 19b, and throughout
the ranges of pressure, fuel concentration, and
strain rate investigated.
We also plot in Fig. 19a the shock-tube
ignition temperatures from Burcat et al. [55],
and in Fig. 19c the corresponding autoignition
temperatures (AIT) taken from the compilation
of Zabetakis [56]. The shock-tube ignition temperatures were estimated from the experimental
data under stoichiometric conditions of fuel/
oxygen mixtures in argon diluent, at the experimental ignition delay times of ;0.3 ms. It is
seen that while the qualitative dependence of
the ignition temperature on fuel structure between the shock-tube experiments and the
present convective-diffusive system share
marked resemblance, the present results do not
follow the trend of the autoignition temperatures of the same fuels. The autoignition experiments benefit from very long residence times,
hundreds of seconds [56] whereas the characteristic residence time in our system is of the
order of milliseconds, and the ignition delay
times in shock-tube experiments are typically
tens or hundreds of microseconds. These differences further support our conclusion that within
the parameter space adopted in our study (with
the exception of the high-pressure regimes II
and III for n-butane and i-butane seen in Fig. 13
and 14), the convective/diffusive ignition is initiated by fuel oxidation following a high-temperature reaction mechanism. For n-butane and
i-butane with p greater than approximately 5
atm, it is tempting to argue that ignition in
regimes II and III is significantly influenced or
dominated by the intermediate- and low-temperature fuel oxidation mechanisms, because of
the significant differences in the p-T responses
from those at lower pressures. This inference,

HYDROCARBON IGNITION IN CONVECTIVE-DIFFUSIVE SYSTEMS

however, needs to be validated in future kinetic
modeling studies.
CONCLUSIONS
We have conducted an extensive experimental
investigation on the nonpremixed ignition characteristics of C2C4 hydrocarbons in an aerodynamically strained flow of opposed cold fuel
versus hot air jets. The ignition responses of
ethane, propane, n-butane, and i-butane were
found to possess a number of similarities, summarized below.
First, flame ignition is preceded by the onset
of chemiluminescent glow, except at high pressures ( p . ;5 atm). This weak light emission is
due to excited formaldehyde and OH, and is
indicative of the existence of mild oxidation, as
substantiated by the numerical modeling of
ethane ignition. Second, similarity exists concerning the effects of external parameters on
ignition. Thus, the ignition temperature initially
decreases with an increase in fuel concentration, but it may reach a constant value at large
fuel concentrations. Increased aerodynamic
straining progressively increases the ignition
temperature, whereas an increase in the system
pressure facilitates ignition overall.
Distinct regimes of pressure sensitivity
emerge for the two butane isomers, which may
correspond to the transition between the lowto-intermediate and high-temperature oxidation mechanisms observed in homogeneous systems. Isobutane is found to be more difficult to
ignite than n-butane, except at the lowest pressures of this study, where the two isomers ignite
at similar temperatures.
Limited kinetic modeling study suggests that
ignition at pressures below 5 atm is initiated by
fuel oxidation following the high-temperature
mechanism of radical chain branching. The lowto-intermediate temperature fuel oxidation kinetics is present in the system, and occurs at a
different spatial location from the region dominated by the high-temperature oxidation kinetics. The low-to-intermediate temperature chemistry contributes little to flame ignition.
Lastly, in our nonpremixed system the ignitability decreases in the order ethane . propane . n-butane . i-butane at 1 atm. This

793

ranking is opposite to the one shown by the

autoignition temperatures. Our future research
will involve detailed modeling of the C3 and
higher hydrocarbons ignition, and a more accurate experimental characterization of the mild
oxidation regimes and their relation to possible
two-staged ignition phenomena.
The authors wish to thank Dr. Y. Tan and Dr.
T. G. Kreutz of Princeton University for help in
connection with the experimental results, and for
the useful technical observations, respectively. We
also wish to acknowledge the fruitful comments of
Dr. C. K. Westbrook. This work was supported by
the Army Research Office under the technical
monitoring of Dr. David Mann.
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Received 19 May 1998; accepted 9 September 1998