Combustion and Flame 157 (2010) 2333–2339

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Combustion and Flame

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c o m b u s t fl a m e

A jet fuel surrogate formulated by real fuel properties

Stephen Dooley a,*, Sang Hee Won a, Marcos Chaos a, Joshua Heyne a, Yiguang Ju a, Frederick L. Dryer a,
Kamal Kumar b, Chih-Jen Sung b, Haowei Wang c, Matthew A. Oehlschlaeger c, Robert J. Santoro d,
Thomas A. Litzinger d
a
Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544, USA
b
School of Engineering, University of Connecticut, Storrs, CT, USA
c
Department of Mechanical, Aerospace, and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, NY, USA
d
Propulsion Engineering Research Center, The Pennsylvania State University, University Park, PA, USA

a r t i c l e i n f o a b s t r a c t

Article history: An implicit methodology based on chemical group theory to formulate a jet aviation fuel surrogate by the
Received 30 June 2010 measurements of several combustion related fuel properties is tested. The empirical formula and derived
Accepted 2 July 2010 cetane number of an actual aviation fuel, POSF 4658, have been determined. A three component surrogate
Available online 23 July 2010
fuel for POSF 4658 has been formulated by constraining a mixture of n-decane, iso-octane and toluene to
reproduce the hydrogen/carbon ratio and derived cetane number of the target fuel. The validity of the
Keywords: proposed surrogate is evaluated by experimental measurement of select combustion properties of POSF
Jet fuel
4658, and the POSF 4658 surrogate.
Surrogate formulation
Kinetic model (1) A variable pressure flow reactor has been used to chart the chemical reactivity of stoichiometric
Group additivity mixtures of POSF 4658/O2/N2 and POSF 4658 surrogate/O2/N2 at 12.5 atm and 500–1000 K, fixing
Fuel properties the carbon content at 0.3% for both mixtures.
Combustion jet-A
(2) The high temperature chemical reactivity and chemical kinetic–molecular diffusion coupling of
POSF 4658 and POSF 4658 surrogate have been evaluated by measurement of the strained extinc-
tion limit of diffusion flames.
(3) The autoignition behavior of POSF 4658 and POSF 4658 surrogate has been measured with a shock
tube at 674–1222 K and with a rapid compression machine at 645–714 K for stoichiometric mix-
tures of fuel in air at pressures close to 20 atm.
The flow reactor study shows that the character and extent of chemical reactivity of both fuels at low
temperature (500–675 K) and high temperature (900 K+) are extremely similar. Slight differences in the
transition from the end of the negative temperature coefficient regime to hot ignition are observed. The
diffusion flame strained extinction limits of the fuels are observed to be indistinguishable when com-
pared on a molar basis. Ignition delay measurements also show that POSF 4658 exhibits NTC behavior.
Moreover, the ignition delays of both fuels are also extremely similar over the temperature range studied
in both shock tube and rapid compression machine experiments. A chemical kinetic model is constructed
and utilized to interpret the experimental observations and provides a rationale as to why the real fuel
and surrogate fuel exhibit such similar reactivity.
Ó 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

1. Introduction formation and engine efficiency in a facile and fundamental scien-

The coupling of computational fluid dynamics with detailed
chemical kinetics provides the promise of optimizing engine per-
formance and exploring the effect of fuel variability on pollutant
* Corresponding author. Address: Department of Mechanical and Aerospace
Engineering, Princeton University, Princeton, NJ 08544, USA.
E-mail address: dooleys@princeton.edu (S. Dooley).
tific manner.
Jet aviation fuels, diesels and gasolines are complex mixtures of
hundreds of chemical components. The detailed numerical simula-
tion of the combustion of real fuels continues to be out of reach
when applied to any fuel which is not a pure component or a mix-
ture of more than a few components. The most prevalent proposal
to circumvent this problem is the use of a surrogate fuel. A surro-
gate should be comprised of only a handful of components but be
capable of emulating the gas phase combustion characteristics of

0010-2180/$ - see front matter Ó 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.combustflame.2010.07.001
2334 S. Dooley et al. / Combustion and Flame 157 (2010) 2333–2339

the real fuel being studied, with the advantage that the resulting Table 1
reaction mechanism is of much more manageable size. This is Proposed surrogate fuel components, molecular structures and formulas.

especially the case considering the recent progress of modern

mechanism reduction techniques, e.g. [1].
Even so, a significant remaining challenge is how to determine a
specific mixture composition to best emulate a specific real fuel of
interest. Though certification tests required for classifying a partic-
ular real fuel for use in power generation applications are numer-
ous, more complex fuel characterizations are generally required to
formulate the surrogate. Moreover, much of the accepted certifica-
tion methodologies, for example, hydrogen content, aromaticity
and cetane index [2] are based upon correlations developed from
historical petroleum derived fuel properties and may therefore
be of limited accuracy when applied to modern fuels. Numerous
surrogate studies, for example [3–5], have however pursued for-
mulations based on these criteria or through empirical adjust-
ments and testing in engines and/or ideal reactors. Given the
compositional variability in real fuels, particularly as non-petro-
leum transportation fuels emerge, it is important to develop sim-
pler prescriptions for matching real fuel and surrogate behavior.
To this end, Ghosh et al. [6,7] have shown that the derived ce-
tane number (DCN) and octane number may be correlated to dis-
tinct molecular fragment groupings rather than to mixtures of
specific components. Similarly, Yang et al. [8], Pepiot-Desjardins
et al. [9] and particularly Yan et al. [10], have developed correlative
techniques for predicting sooting propensity of fuels based upon
individual contributions of distinct molecular fragment groups.
Both concepts are similar in philosophy to group additivity meth-
ods [11] that are commonly used to estimate thermochemical
properties, but due to the complexity of the controlling processes
there are no pedagogical ‘‘rules” based upon theory for predicting
derived cetane ignition or sooting. The logical extension of these
studies is to suggest that important fuel combustion properties by simple experimental determinations. This study takes an exem-
should be predictable based upon an additive relationship of plary case of a real jet-A of intended average composition, POSF
empirically derived chemical group fragment properties. 4658. Basic characterization is performed and the combustion
Building on these works, we have concentrated upon founda- behaviors of the real fuel as well as that of a surrogate mixture
tional methodologies to which additional components and com- formulated by the described methodology, are measured in flow
plexities can be added to refine property emulation and to reactor, shock tube, rapid compression machine, and strained
eventually include emulation of physical properties such as distil- extinction experiments. To allow for interpretation of our experi-
lation curve. We initially choose autoignition, heat release rate, mental data and to help assess the accuracy of available kinetic
adiabatic flame temperature, local mixing-limited stoichiometric models under blended conditions, the proposed POSF 4658 surro-
constraint, extinction, and sooting behavior, to be the important gate is limited in composition to n-decane, iso-octane and toluene.
combustion property targets. From these, we hypothesize the need These are the components of Table 1 for which the highest fidelity
to emulate real fuel hydrogen-to-carbon-ratio (H/C), a measure of kinetic models and most exhaustive validation data are available.
sooting propensity, a measure of overall chemical kinetic autoigni-
tion quality, and the average molecular weight using the chosen
surrogate mixture components in proper composition. 2. Experimental
DCN [12–14] and smoke point (or threshold sooting index, TSI)
[8,15] are two simply determinable global combustion parameters The experimental devices used have been discussed in detail
selected to satisfy the above rationale. A description of these param- previously, and are only briefly described herein. Tabulated exper-
eters and of their respective significance is outlined by Xu et al. [16] imental data for all measurements are available in the Supplemen-
and elaborated in the Supplementary materials. These parameters tary materials.
may be reproduced by a number of combinations of a number of
different components to form a surrogate mixture. Our proposed 2.1. Derived cetane number measurements, DCN
palette of surrogate components represents each of the generic clas-
ses of molecular structure found in existing aviation fuels, Table 1. To Derived cetane number (DCN) measurements were performed
take advantage of the substantial amount of previous experimental using an ignition quality testing (IQT) apparatus [13,14] with the
and kinetic modeling work on this topic, where ever possible our ASTM 6890 [12] procedure for determination of autoignition char-
proposed components share a large degree of similarity with those acteristics of diesel fuels. The IQT determines an experimental igni-
that have already been proposed or studied by other researchers tion delay of a fuel spray in a pressurized (22.1 atm) and heated
e.g. [3–5]. This approach ought to allow for the more expedient (833 K) constant volume chamber of air. The derived cetane num-
development of accurate chemical kinetic models. ber is obtained using a correlation provided by ASTM [12]. The
Here we demonstrate some simple parameterizations for surro- measurements reported here are the average of thirty-two individ-
gate formulation and show that with careful choices of surrogate ual experimental measurements on at least three individual fuel
components, surrogates can be formulated to replicate these samples and lie within a standard deviation of ±0.6 DCNs of the re-
important chemical kinetic combustion properties of the real fuel ported value. DCNs are determined for binary and ternary mixtures
 S. Dooley et al. / Combustion and Flame 157 (2010) 2333–2339 2335

of n-decane, iso-octane and toluene. In all, fourteen different mix- (+M) = C2H6 (+M). The ethane consumption and higher hydrocar-
tures were investigated, Table S1, Supplementary materials. bon chemistry is described by a C2–C4 submechanism that was re-
cently validated by Healy et al. [23]. The description of our base
chemistry is completed by the incorporation of the work of Laskin
2.2. Surrogate formulation
et al. [24] which describes the higher alkenyl type species, such as
butadiene. To describe mass transport, Lennard–Jones parameters
The empirical formula of POSF 4658 was determined experi-
have been estimated largely based on those recommended in a re-
mentally (Perkin Elmer 2400 Series II CHN analyzer) employing
view conducted by Mourits et al. [25], and correlated to molecular
ASTM method D5291 to be C10.17H19.91 (H/C = 1.957). The DCN of
weight in a similar manner to Wang and Frenklach [26] for the
POSF 4658 determined using the same IQT testing method de-
ready estimation of collisional diameter and energy well depth of
scribed above is 47.1 ± 0.3, and the TSI was determined using the
the species composing the kinetic model. A more detailed descrip-
smoke point technique [8] to be 21.4 (personal communication,
tion of model construction and of the modeling assumptions em-
Santoro, R.J.). These data provide four constraints which within
ployed to compare computations to experimental observations is
the present methodology a surrogate should emulate, DCN, H/C,
provided in the Supplementary materials.
TSI and an average ‘molecular’ mass of 142 ± 5 g/mol.
The data presented in Table S1, have been delineated by an ex-
treme vertices matrix to parameterize the DCN, H/C, MW and TSI 4. Results and discussion
as a function of n-decane, iso-octane and toluene mole fraction.
Available TSI data for pure components [17] were utilized with a 4.1. Variable pressure flow reactor
linear relationship between TSI and mixture fraction for binary
and ternary mixtures. Though the four targets can be approxi- A detailed description of this device and its operation is given in
mated with the mixtures of the surrogate components listed in [27]. The reactivity of both POSF 4658 and surrogate over the tem-
Table 1, indeed, this has been shown for real fuel TSI [10], it is perature range, 500–1000 K, were determined to compare low,
not possible to compute a mixture formula of n-decane/iso-oc- intermediate temperature and hot ignition kinetic behavior. Mea-
tane/toluene in any proportion that satisfies the H/C ratio and TSI surements of oxygen, carbon dioxide, carbon monoxide, and water
constraints simultaneously. Furthermore, mixtures of the three mole fractions and heat release (DT) as a function of initial reaction
components investigated here cannot match the molecular weight temperature (in 25 K steps) and fixed reaction time (1.8 s) were ob-
constraint. The experimental validations investigated herein are tained at constant pressure (12.5 atm). Fuel-dilute conditions were
predominately chemical kinetic in nature and therefore more utilized to approximate adiabatic reaction conditions. Carbon con-
strongly influenced by the H/C ratio than by the TSI constraint. centrations of 0.3 mol.% were utilized in both real fuel and surro-
Hence in the context of the present study H/C ratio is allowed pre- gate mixture experiments. The slight differences in average
cedence over TSI. A three component n-decane/iso-octane/toluene molecular weight of real and surrogate fuels (C8.61H17.27 vs.
mixture of 42.67/33.02/24.31 mol.% is predicted to have a DCN of C10.17H19.91) results in slightly different oxygen concentrations
47.1 and a TSI of 14, is of H/C 2.01 and average ‘molecular’ mass (0.45 mol.% vs. 0.447 mol.%) at stoichiometric reaction conditions.
of 120.67 g mol 1. This mixture was prepared on a mass basis Estimated measurement uncertainties are ±5% (no less than
and we label it as the POSF 4658 surrogate. The DCN of the POSF 30 ppm) in reported speciation, ±5 K in reported temperatures,
4658 surrogate was measured as 47.4 ± 0.3, indicating the applica- ±0.2 atm in reported pressures, and ±0.01 s in reported reaction
bility of our DCN correlation. time. In conjunction with the kinetic model these detailed mea-
surements allow for an analysis of the chemical processes which
effect overall fuel reactivity in each regime.
3. Kinetic model
4.2. 500–625 K low temperature chemistry
Presently a kinetic model which describes the oxidation of all
three surrogate components is unavailable. Therefore, a detailed Fig. 1 shows the extent of oxidation for both fuels in the low
chemical kinetic model for the POSF 4658 surrogate has been temperature region to be very similar both in character and
assembled to help interpret our experimental observations. The
surrogate fuel chemistry is described by combining three recent
individual kinetic models; the toluene model of Metcalfe et al.
[18], the n-alkane chemistry of Westbrook et al. [19] and the iso-al-
kane chemistry of Mehl and co-workers. [20]. Cross reactions
involving high molecular weight fuel radicals are not considered
in the kinetic model which only allows fuel components to interact
through their respective influence on the small species population.
In the case where there has been a conflict or duplication of nomen-
clature, chemistry or thermodynamic parameters between the
three individual component sub-models, chemical reaction rate
constant and thermodynamic parameters have been chosen in the
following preferential order; Metcalfe et al. > Mehl et al. > West-
brook et al. Presentation of a detailed assessment and analysis of
the validity of the kinetic model is beyond the scope of the present
study. However, simulations performed with the combined model
show very similar results against those of the original models when
exercised at similar conditions to those of the current study.
The C0–C4 submechanism that forms the basis for the chemical
kinetic model is that which was assembled and tested for toluene Fig. 1. Flow reactor oxidation data for conditions of 12.5 atm, 0.3% carbon, u = 1.0
oxidation [18]. Briefly it consists of the H2/O2 [21] and C1 chemistry and s = 1.8 s, for POSF 4658 (symbols), POSF 4658 surrogate (solid lines) and model
of Zhao et al. [22] up to and inclusive of the reaction CH3 + CH3 simulation of POSF 4658 surrogate (dashed lines), inset; DT.
2336 S. Dooley et al. / Combustion and Flame 157 (2010) 2333–2339
magnitude; the oxidation of POSF 4658 is onset at 550–578 K, the
rate of oxidation increases until 623–648 K, where the fuel exhibits
negative temperature coefficient (NTC) behavior. The POSF 4658
surrogate shows the onset of reactivity at 564–589 K and exhibits
NTC behavior at 613–636 K. The extent of reactivity is reflected by
the amount of O2 consumed and of CO2, CO and H2O formed. Given
the estimated experimental uncertainties, both fuels exhibit very
similar reactivity (all measurements agree to ±15%) and certainly
satisfactory emulation of reactivity in this temperature regime un-
der the conditions studied.
The kinetic model reproduces the qualitative features of the
POSF 4658 surrogate oxidation very well, although the extent of
reactivity in the NTC regime is characteristically over-predicted.
Both model and surrogate show the point of highest reactivity in
the low temperature regime at approximately 600 K. It has previ-
ously been established under very similar conditions to those of
the present study, that iso-octane e.g. [28] and toluene e.g. [18]
are not capable of sufficient radical-chain branching activity to
support oxidation below approximately 800 and 900 K, respec-
tively. Analysis of the model simulations at 600 K support this con-
clusion, showing at s = 1.8 s only 2.2% of the initial mole fraction of
n-decane remains, compared to 37.3% and 60.2% of the initial mole
fractions of iso-octane and toluene respectively. At the much later
time of 3.6 s, model predictions show iso-octane and toluene mole
fractions remain largely unchanged (35.4% and 59.0%, respec-
tively); at these low temperatures, aromatic and iso-alkane compo-
nents are oxidized by the radical pool generated by the n-alkane,
and in turn, generate few active radicals themselves.
The similarity in reactivity exhibited by model, surrogate and
POSF 4658 at this condition is extremely encouraging. It appears
that the n-alkane component of the surrogate is behaving in a very
similar way to the more complex mixture of n-alkyl components
present in POSF 4658, Fig. 1. Therefore it is strongly suggestive that
the prescribed quantity of n-decane is accurately emulating the
chemical processes of the total n-alkyl components in the real fuel.
Moreover, it appears that the aromatic and iso-alkane components
are also present in appropriate quantities to provide the intended
radical termination processes sufficiently so as to replicate the glo-
bal reactivity of the real fuel.
4.3. 625–825 K negative temperature coefficient
POSF 4658 exhibits NTC behavior in the temperature range
623–648 to 723 K, Fig. 1. At 723 K little or no conversion of oxygen
or formation of products are observed, indicating that the reactiv-
ity of the system has halted almost entirely under these conditions.
Subsequently, 723–771 K, the systems shows very modest reactiv-
ity as exhibited by the O2 and H2O profiles, before showing a much
larger increase in reactivity at 771–798 K (hot ignition condition).
The POSF 4658 surrogate emulates the temperature dependence of
the target fuel very well with regard to the NTC regime. However
the fuels deviate in reactivity between 723 and 771 K, with the sur-
rogate remaining un-reactive until 787 K, i.e. a temperature
approximately 54 K higher than the real fuel.
At 800 K, the model again shows the surrogate fuel to be con-
sumed from radicals that are largely generated through the activity
of the n-alkane component, only 25% of which remains at this reac-
tion time (vs. 71% iso-octane and 85% toluene). By virtue of this
deviation in reactivity, we may surmise that the much richer
molecular structural palette contained in the real fuel allows POSF
4658 to become oxidized at the lower temperatures of the inter-
mediate temperature regime. The functional temperature depen-
dence of chemical reactivity results from a complex switching of
the fate of alkyl, alkylperoxy and hydroperoxy alkyl radicals which
is dependent in a detailed manner on molecular structure. Recogn-
ising this, the modest divergence in reactivity between real fuel
and such a simple surrogate is not discouraging. In fact, given the
much simpler molecular structure of the surrogate fuel it is extre-
mely encouraging that it should emulate the more diverse real fuel
composition so closely in regard to the complex temperature
dependence of combustion oxidation kinetics, particularly so in
reference to the exit of the NTC region.
It is likely that in our provisional surrogate the iso-alkane com-
ponent, is in fact too highly branched to emulate very precisely the
reactivity of the much lesser branched alkanes that are present in
POSF 4658 [2] at these temperatures of transitioning regimes of
chemistry. The other contributing factor involved at these condi-
tions is in the selection of toluene as representative of the generic
aromatic class of compounds. The longer alkyl chain(s) of the aro-
matics found in real jet aviation fuels [2] ought to allow these moi-
eties to become oxidized at much lower temperatures than
toluene. We view these as relatively minor deficiencies especially
as our ‘‘first generation” surrogate components allow a much more
thorough understanding via analyses provided by more reliable ki-
netic models than those that exist for alternative components. The
incorporation of one or more n-alkyl aromatics or perhaps a simi-
larly reactive, better studied, compound such as a xylene, would al-
low the surrogate to emulate the reactivity of the real fuel with
improved fidelity.
4.4. 825–1050 K intermediate to high temperature chemistry
Fig. 1 shows that the reactivity of the POSF 4658 surrogate re-
mains diminished relative to POSF 4658 until temperatures greater
than approximately 900 K. Although the kinetic model reproduces
these measurements quite well, it is noted that at temperatures
above 900 K carbon monoxide is under-predicted and carbon diox-
ide over-predicted relative to experiment. Analysis of the chemical
flux at 950 K shows that both alkane components are consumed al-
most completely by typical high temperature hydrogen abstraction
alkyl radical beta-scission processes, with iso-octane showing a
small (5%) level of unimolecular decomposition. This chemistry is
in contrast to the rather more complex competition between
beta-scission and addition of O2 to alkyl radicals that are formed
below 900 K. This may be a significant observation as the reactivity
of the ternary system at these higher temperatures depends largely
on the identity and quantity of beta-scission products formed.
Since POSF 4658 and surrogate share similar species evolutions,
it is likely that the net reactivity (radical producing/consuming
abilities) of the intermediates formed by both fuels culminating
in the crucial formation and decomposition of H2O2 are approxi-
mately equal in this temperature range.
4.5. Diffusion flame extinction limits
A counterflow burner was utilized to measure the extinction
strain rate as a function of nitrogen dilution for POSF 4658 and
the proposed POSF 4658 surrogate for diffusion flames. The tem-
perature of the fuel side was maintained at 500 ± 5 K, and that of
the oxidizer (air) side at 298 K ± 2 K, in an identical setup to Won
et al. [29]. In addition to being an important property to under-
stand the stabilization mechanism of a turbulent flame, extinction
limits of diffusion flames are commanding in practical combustion
systems, and thus necessary for a surrogate to satisfy.
Fig. 2 shows that the extinction behavior exhibited by POSF
4658 is very closely emulated by the surrogate when evaluated
on a mole fraction basis. Also shown are computations performed
by a reduced kinetic model produced by the path flux analyses
technique [30]. The model reproduces the extinction strain rate
quantitatively very well, though predictions at higher mole/mass
fractions under predict experiment by up to 14%. It has been dem-
onstrated that the extinction limit of diffusion flames have a linear
 S. Dooley et al. / Combustion and Flame 157 (2010) 2333–2339
Fig. 2. Strain rates of extinction for counter flow diffusion flames at 1 atm, POSF
4658 (solid symbols), POSF 4658 surrogate (hollow symbols) and POSF 4658
surrogate model simulation (lines).
dependence on the OH radical concentration due to its dual role as
a chain-branching agent and in heat production [29].
Model simulations show that as strain rate is increased, OH con-
sumption by interaction with iso-alkane and in particular aromatic
fuel fragments increases, (C3–C6 species, Fig. S8, Supplementary
materials). Under flame conditions, the toluene derived fragments
do not support chain branching as prominently as n-alkyl or iso-al-
kyl fragments and these reactions lead to decreased radical-chain
branching rate through consumption of OH predominantly by
chain-propagation. It has previously been shown that the growth
of the radical pool in binary-fuel flame systems is governed by
the kinetic coupling of radical production/consumption pathways
of each fuel component [29]. Therefore the similar flame extinction
behavior of both fuels indicates that the overall radical production/
consumption rate of POSF 4658 flames is closely emulated by the
proposed three component surrogate.
However, when the extinction data are analyzed in terms of fuel
mass fraction, there is an obvious divergence in behavior Fig. 2. This
apparent discrepancy may be explained by the lower average
molecular weight of the surrogate compared to that of POSF
4658, 120.67 g mol 1 vs. 142.01 g mol 1. It is anticipated that this
discrepancy will not exist for surrogate mixtures with a more com-
parable average molecular weight, as postulated in previous works
[31,32]. The use of larger components from the same chemical
functional class will allow the average molecular weight of the real
fuel to be additionally emulated by a surrogate. Nevertheless, it is
clearly demonstrated that the extinction limit of diffusion flames
can be properly emulated by the current methodology of surrogate
formulation.
4.6. Ignition delay
Ignition delay times of stoichiometric mixtures of POSF 4658
and the POSF 4658 surrogate in air, (i.e. 1.368/20.72/77.92 mol.%
POSF 4658/O2/N2 and 1.599/20.67/77.73 mol.% POSF 4658 surro-
gate/O2/N2) were measured near 20 atm in both a shock tube and
a rapid compression machine (RCM).
4.7. Shock tube
The ignition behavior of both fuels has been examined at pres-
sures of 16–25 atm, reflected shock temperatures of 674–1222 K.
2337
The operation of this heated device with low vapour pressure fuels
has been described previously by Shen and Oehlschlaeger [33]. Tai-
lored driver gas mixtures of N2/He were used to extend the re-
flected shock test times for the measurement of ignition delay at
the lower end of the examined temperature range; measurements
made at long test times show well behaved pressure profiles with
relatively small levels of viscous-induced pressure rise, in the
range of (dp/dt) = 0–2% ms 1, see Supplementary materials. Ignition
delay times were measured using endwall OH emission and side-
wall pressure measurements as previously described [33]. Thermo-
dynamic properties for jet-A, the three surrogate components, O2
and N2 were taken from the Burcat and Ruscic database [34] and
used for determination of reflected shock temperature and pres-
sure, the uncertainties of which are discussed in the Supplemen-
tary materials.
4.8. Rapid compression machine, RCM
A heated RCM has been used to obtain ignition delay measure-
ments of both fuels at 22.3 atm over the compressed temperature
range 639–721 K. This device and its mode of operation with low
vapour pressure fuels has been described previously [35,36].
In the RCM experiments the compressed gas temperature and
the ignition delay are inferred from the measured pressure history
[35], using the same thermodynamic properties as the shock tube
study. The definition of the ignition delay is based on the occur-
rence of an inflection point in the pressure history during the pres-
sure rise due to ignition [35], see Supplementary materials. The
RCM data presented in Fig. 3 are for the main ignition event. Each
measurement is the average of four individual experiments, which
generally show excellent repeatability. Ignition delays with stan-
dard deviations and an example of experiment to experiment
repeatability are also reported in the Supplementary materials.
All ignition data are presented in Fig. 3. Shock tube measure-
ments show that POSF 4658 exhibits NTC behavior, onset at
797 K and terminating at 904 K in general agreement with the
observations of Vasu et al. [37] who has studied POSF 4658 under
similar conditions. See Supplementary materials for a more de-
tailed comparison with previous jet fuel ignition studies. Good
agreement for both fuels exists for ignition times at the lowest
temperatures accessible in the shock tube with those measured
Fig. 3. Ignition delay times for POSF 4658 16.3–24.8 atm (solid symbols), POSF
4658 surrogate 17.7–22.9 atm, (hollow symbols) and model simulation of POSF
4658 surrogate (lines). Black data correspond to shock tube measurements/
simulations, red data correspond to RCM measurements/simulations.
2338 S. Dooley et al. / Combustion and Flame 157 (2010) 2333–2339
in the RCM. The authors recognize that shocktube and RCM data
are not strictly comparable and this is clearly discernable from
model simulations also plotted in Fig. 3. Shock tube ignition times
are 10–30% shorter than those observed in the RCM. This is attrib-
uted to differences in the pre-ignition pressure behavior character-
istic of the two experiments, particularly to post compression heat
losses in the RCM, leading to slightly longer ignition times.
At comparable conditions, the maximum difference in delay
time between POSF 4658 and surrogate is 30%, indicative of the su-
perb capability of this particular surrogate for emulating real fuel
behavior under practical propulsion engine conditions. These data
further demonstrate the validity of the proposed surrogate formu-
lation technique and of the applicability of the underlying princi-
ples of chemical group additivity.
In reference to kinetic model simulations of shock tube data, it
is important to recognize that the model should reproduce the flow
reactor observations quite well yet consistently predict slower
ignition delay times by approximately a-factor-of-two relative to
ignition experiments. More precisely, for an example surrogate
experiment at 962 K, Fig. 3 shows the surrogate to have exited
the NTC region yet the model predicts ignition at 962 K to be inside
the NTC regime. Simulations accounting for the viscous-induced
pressure rises of 0.4 atm ms 1 do not significantly alter the com-
puted ignition delays. Given the evident disagreement between
model and experiment we interpret the model results with cau-
tion. Notwithstanding this, the simulated ignition delay time for
this condition is 3200 ls. At a time of 2800 ls, the model shows
that the temperature has risen to 1044 K and that 15.5%, 53.3%,
77.1% of the respective initial concentrations of n-decane, iso-oc-
tane and toluene remain. Consistent with model analysis of the
other environments, the n-alkyl component is largely responsible
for radical production during surrogate oxidation, and by extension
also in POSF 4658.
Much more fuel is present in the ignition simulations compared
to the flow reactor simulations, 6851/5303/3903 vs. 149/115/
85 ppm n-decane/iso-octane/toluene, respectively. It is possible
that any in-accurately assigned reaction rate constants describing
crucial branching ratios might propagate an error, and manifest
in larger deviations from experiment when more fuel is present.
For example the elongated NTC behavior shown by the model
may be due to an under-emphasis on beta-scission of n-decyl/alkyl
radicals leading to exaggerated low temperature chemistry pro-
cesses to the detriment of high temperature chain branching. This
conclusion is supported by analysis of the model simulation at this
condition which shows a strong competition for n-decyl alkyl rad-
icals between beta-scission (approximately 40%) and formation of
RO2 (approximately 60%), with almost all of the RO2 formed en-
gaged in radical chain-propagation processes. Given this analysis,
it appears again that the most important facet in the accurate
numerical simulation of a jet fuel surrogate is in the accurate
description of n-alkyl chemistries, not only confined to alkanes
themselves but also to any alkyl aromatics or lightly branched
alkanes.
The RCM ignition experiments are noteworthy in that while the
overall autoignition delay times of the real fuel and its surrogate
are very similar, the quality of ignition differs markedly. The key
distinguishing feature is the existence of a rather strong pseudo-
first-stage ignition activity (s1) for POSF 4658, while the surrogate
does not show first-stage ignition, Fig. S3. The other distinguishing
feature is the higher post ignition rate of pressure rise for the sur-
rogate mixture, consistent with a more sudden ignition event. Ki-
netic model computations account for heat losses by the
consideration of the full pressure history of non reactive mixtures
of identical Cp/Cv (c) as described by Mittal and Sung [35] and
reproduce the quality of RCM data very well, Figs. 3 and S5. How-
ever, consistent with shock tube simulations, the model predicts
the main ignition event to occur at longer times than experiment,
by approximately a-factor-of-two. The emulation of two-stage
POSF 4658 ignition would appear to be extremely challenging
and will likely require a surrogate of more structurally diverse
chemical fragments than those generated by a simple mixture of
n-decane, iso-octane and toluene.
5. Conclusions
This study outlines a method for the formulation of a fuel spe-
cific jet fuel surrogate via the empirical correlation of relatively eas-
ily measurable fuel properties. In so doing we predict the surrogate
fuel to mimic wide ranging combustion properties of a target real
fuel. This philosophy is tested by the formulation of a surrogate for
the real life jet-A, POSF 4658 by the emulation of DCN and H/C
only. Although demonstrated here for a jet aviation fuel, the de-
scribed methodology of chemical group additivity ought to be
applicable to the study of fuels elsewhere on the distillation curve,
including gasolines and diesels as well as to emerging synthetic
fuels. The proviso qualification being that the surrogate component
palette supports the formation of the distinct chemical functional-
ities formed by the oxidation of the target fuel.
The presented experiments show that the POSF 4658 surrogate
closely emulates the chemical kinetic related behavior of POSF
4658 beyond expectation, supporting considerable optimism that
surrogates composed of somewhat larger molecular weight al-
kanes and alkyl aromatics can lead to further improvements in sur-
rogate performance. It is anticipated the addition of TSI as a further
constraint will allow emulation of the sooting propensity of the
real fuel and also improve and extend the ability for a surrogate
to emulate more global combustion parameters with improved
precision. Moreover, the ignition and diffusion flame strained
extinction studies comparison in particular, lends strong credence
to the proposed surrogate formulation method for application to
the study of practical combustion systems.
It is likely that simple surrogate fuels, such as the first genera-
tion test-case presented here will be deficient in emulating high-
detailed observations of real fuels such as detailed speciation and
two-stage ignition character. Emulation of common small molecu-
lar weight intermediate species such as ethylene and formalde-
hyde may be much more achievable given the intrinsic roles of
these species in regulating chemical reactivity. Indeed, although
the tested surrogate emulates overall ignition times, it fails to
emulate the two-stage ignition behavior exhibited by POSF 4658
in the RCM study. This is not surprising as the surrogate was not
formulated to do so. Such targets may be achievable if an increased
diversity of molecular structure is present in the surrogate compo-
nent palette or/and if additional constraints can be added for sur-
rogate formulation. One such additional constraint might be
through modifications of the IQT testing procedures.
A kinetic model for the presented n-decane/iso-octane/toluene
POSF 4658 surrogate has been constructed and its computations
compared with experimental observations to elucidate similarities
in the reactivity of surrogate and real fuel. Analysis shows that the
chemical reactivity of the surrogate is strongly dependent on the
processes of its n-alkane component. At lower temperatures, the
dependence on n-alkyl radical kinetics is so strong that the fate
of iso-alkyl and aromatic radicals formed in competing abstraction
reactions are in comparison of little consequence. By this virtue,
the accurate numerical modeling of any multi component surro-
gate fuel depends crucially on the accurate description of n-alkyl
chemistry. Finally, although the present first generation surrogate
does not allow simultaneous emulation of H/C, DCN, and TSI, the
use of a higher carbon number alkane such as n-dodecane can
accommodate sufficient addition of aromatic components to
 S. Dooley et al. / Combustion and Flame 157 (2010) 2333–2339
emulate the entire spectrum of fuel properties that are known for
various real gas turbine fuels [16]. Further demonstrations of uti-
lizing these concepts to emulate real fuel combustion kinetic prop-
erties are underway.
Acknowledgments
Work at PU, PSU and UC is part of MURI collaboration supported
by the Air Force Office of Scientific Research under Grant Number
FA9550-07-1-0515. Work at RPI is supported by AFOSR Grant
Number FA9550-07-1-0114, both programs are monitored by Dr.
Julian Tishkoff. We are grateful for collaborative discussions with
Prof. Kenneth Brezinsky, University of Chicago. We are also grateful
to Dr. Tim Edwards, for the provision of POSF 4658, to Dr. Marco
Mehl, Lawrence Livermore National Laboratory and his co-workers
for making their latest iso-alkane kinetic model available to us
prior to publication. Mr. Wenting Sun, Princeton University is
appreciated for discussions on model reduction.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.combustflame.2010.07.001.
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