Combustion and Flame 155 (2008) 380–408

www.elsevier.com/locate/combustflame

Formulation reproducing the ignition delays simulated by a

detailed mechanism: Application to n-heptane combustion
Bruno Imbert a,∗ , Fabien Lafosse b , Laurent Catoire b ,
Claude-Étienne Paillard b , Boris Khasainov c
a LENI, IGM, STI, EPFL, Station 9, CH-1015 Lausanne, Switzerland
b ICARE, CNRS, and University of Orléans, 1C Av. de la Recherche Scientifique, F-45067 Orléans, France
c LCD, CNRS, ENSMA, 1 Av. Clément Ader, F-86961 Futuroscope, France

Received 9 August 2007; received in revised form 30 January 2008; accepted 7 May 2008

Abstract
This article is part of the project to model the kinetics of high-temperature combustions, occurring behind
shock waves and in detonation waves. The “conventional” semi-empirical correlations of ignition delays have
been reformulated, by keeping the Arrhenius equation form. It is shown how a polynomial with 3N coefficients
(where N ∈ [1, 4] is the number of adjustable kinetic parameters, likely to be simultaneously chosen among the
temperature T , the pressure P , the inert fraction X Ar , and the equivalence ratio Φ) can reproduce the delays
predicted by the Curran et al. [H.J. Curran, P. Gaffuri, W.J. Pitz, C.K. Westbrook, Combust. Flame 129 (2002)
253–280] detailed mechanism (565 species and 2538 reactions), over a wide range of conditions (comparable with
the validity domain). The deviations between the simulated times and their fits (typically 1%) are definitely lower
than the uncertainties related to the mechanism (at least 25%). In addition, using this new formalism to evaluate
these durations is about 106 times faster than simulating them with S ENKIN (C HEMKIN III package) and only 10
times slower than using the classical correlations. The adaptation of the traditional method for predicting delays is
interesting for modeling, because those performances are difficult to obtain simultaneously with other reduction
methods (either purely mathematical, chemical, or even mixed). After a physical and mathematical justification
of the proposed formalism, some of its potentialities for n-heptane combustion are presented. In particular, the
trends of simulated delays and activation energies are shown for T ∈ [1500 K, 1900 K], P ∈ [10 kPa, 1 MPa],
XAr ∈ [0, 0.7], and Φ ∈ [0.25, 4.0].
© 2008 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Keywords: Kinetics; Mechanism reduction; Ignition delays; Modeling; Detonation; Shock; n-Heptane

1. Introduction

1.1. General context: n-Heptane autoignition and

detonation

* Corresponding author. Fax: +41 (0) 21 693 35 02. Previous articles [1–4] have aimed at providing a
E-mail address: bruno.imbert@epfl.ch (B. Imbert). kinetic database able to contribute to the choice of a
0010-2180/$ – see front matter © 2008 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.combustflame.2008.05.011
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
Nomenclature
Subscripts
1 initial state of the driven section gas
5 state of the driven section gas behind the
reflected shock
CJ established according to the Chapman–
Jouguet model
cor related to a correlated term (index some-
times omitted to shorten the expression)
exp associated to an experimental measure-
ment
i related to induction (process similar to
autoignition in the case of a detonation)
min minimum
max maximum
opt optimum (minimum or maximum)
Reac linked to the reactive part (fuel and oxy-
gen) of a flammable mixture
ref related to a reference state:
T ref = 1700 K, P ref = 100 kPa, Φ ref =
1.0 and X Ar, ref = 0
sim associated to the predictions simulated
by a kinetic mechanism (here detailed)
vN bounded to the average conditions be-
hind the detonation front, according to
the ZND model
Variables (Latin and Greek letters)
[Y] molar concentration of species Y
(mol m−3 )
A pre-exponential factor (s m3 · (α+β+γ )
mol−(α+β+γ ) )
D detonation celerity (m s−1 )
Da Damköhler number, i.e., the ratio of
the speeds related to the chemical pro-
cesses and the mass transfers (dimen-
sionless)
Ea activation energy (kJ mol−1 )
Gτcor standard geometrical deviation between
a set of reference simulated delays τ sim ,
and times τ cor correlating them (Ap-
pendix A.4) (dimensionless)
i index related to LP (dimensionless)
IT reduced variable related to the inverse of
the temperature T (Section 3.6) (dimen-
sionless)
j index related to LX (dimensionless)
k index related to LΦ (dimensionless)
l index related to one condition (thermo-
dynamic state and composition) (dimen-
sionless)
LP reduced variable related to the logarithm
of the pressure P (Section 3.6) (dimen-
sionless)
381
LT reduced variable related to the logarithm
of the temperature T (Section 3.6) (di-
mensionless)
LX reduced variable related to the logarithm
of the inert fraction X Ar (Section 3.6)
(dimensionless)
LΦ reduced variable related to the logarithm
of the equivalence ratio Φ (Section 3.6)
(dimensionless)
Lτ reduced variable related to the logarithm
of the ignition delay τ (dimensionless)
M number of conditions used for the kinetic
database (dimensionless)
M matrix (dimensionless)
MY molar mass of species Y (g mol−1 )
n unspecified integer (dimensionless)
N number of adjustable parameters (di-
mensionless)
p pressure coefficient (dimensionless)
P pressure (bar or kPa)
R = 8.314 gas constant (J mol−1 K−1 )
T temperature (K)
x implicit dilution coefficient (dimension-
less)
XY molar fraction (or percentage) of species
Y (argon, if Y not expressed with X in
index) (dimensionless or %)
u particle velocity expressed in the refer-
ential related to the shock wave front
(m s−1 )
V vector (dimensionless)
α partial pseudo-order related to n-heptane
(dimensionless)
β partial pseudo-order related to oxygen
(dimensionless)
γ partial pseudo-order related to argon (di-
mensionless)
i induction distance (m)
τcor standard (arithmetic) deviation between
a set of reference simulated delays τ sim ,
and times τ cor correlating them (dimen-
sionless)
Φ equivalence ratio of the flammable mix-
ture (dimensionless)
λ average cell width of a self-sustained
detonation (mm)
θa activation temperature (K)
ρ density (kg m−3 )
τ ignition delay (or induction time in the
detonation case) (s)
382 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
Acronyms and abbreviations
CFD computational fluid dynamics
CJ Chapman–Jouguet [8,9]: “0D” thermo-
dynamic detonation model
CSP computational singular perturbation
fy (z) multivariable function, only dependent
on z by fixing the parameter y
ILDM intrinsic low-dimensional manifold
liquid fuel appropriate to the pulsed detonation engine
(PDE). With this intent, a model molecule, easier and
safer to transport than a gas (such as ethylene, which
is well designed to supply this new kind of propulsion,
according to Desbordes et al. [5]) has been investi-
gated. The high-temperature combustion and the det-
onation of gaseous premixed n-heptane/oxygen mix-
tures have been experimentally and numerically char-
acterized, taking into account the four following as-
pects.
(1) To better understand the oxidation process, ig-
nition delays τexp ∈ [37 µs, 680 µs] have been
measured behind reflected shock waves in a
shock tube (test section: inner diameter close
to 76 mm ≈ 3.0 and length about 4500 mm ≈
177 ) [1], under the following experimental con-
ditions:
• high temperatures T5 ∈ [1290 K, 1600 K] ≈
[1015 ◦ C, 1325 ◦ C] ≈ [1860 ◦ F, 2420 ◦ F];
• pressures P5 ∈ [250 kPa, 720 kPa] = [2.5 bar,
7.2 bar] ≈ [36 psi, 104 psi];
• equivalence ratios Φ ∈ [0.5, 1.5];
• high dilution in argon: XAr ∈ [0.88, 0.99].
(2) Several oxidation mechanisms have been tested
to simulate these delays τ exp using S ENKIN
(C HEMKIN III package) [1]. In particular, the
Curran et al. detailed model [6,7], composed of
565 species and 2538 reactions, has shown good
agreement with experiments. To decrease the dis-
crepancy (typically by a factor 2 down to 1.25),
five constant rates have been adjusted within their
validity range. The resulting model, designed as
the “modified mechanism,” is considered for this
investigation.
(3) Self-sustained detonations have been experimen-
tally studied in the same shock tube [2–4], using
n-heptane/oxygen mixtures:
• initially at room temperature T1 ≈ 295 K ≈
20 ◦ C ≈ 70 ◦ F;
• at initial pressure P1 ∈ [200 Pa, 14 kPa] =
[2.0 mbar, 140 mbar] ≈ [0.03 psi, 2.0 psi];
• at equivalence ratios Φ ∈ [0.4, 2.5];
• diluted or not in argon: XAr ∈ [0, 0.7].
lg decimal logarithm ⇔ lg(10) = 1
ln neperian logarithm ⇔ ln(e) = 1
NTC negative temperature coefficient
PDE pulsed detonation engine
QSSA quasi-steady state approximation
RRKM Rice–Ramsperger–Kassel–Marcus [32]:
model of chemical reactivity
ZND Zel’dovitch–von Neumann–Döring [10–
12]: “0D” kinetic detonation model
First, the detonation velocities D exp have been
measured and compared to the theoretical val-
ues D CJ , predicted by the Chapman–Jouguet
model [8,9]. These speeds Dexp ∈ [1800 m s−1 ,
2400 m s−1 ] ≈ [6500 km h−1 , 8650 km h−1 ] ≈
[4050 mph, 5350 mph] correspond to Mach num-
bers between 5.9 and 9.4 (the sound speed ranges
from 305 m s−1 ≈ 1100 km h−1 ≈ 680 mph at
Φref ≈ 0.4, down to 255 m s−1 ≈ 920 km h−1 ≈
570 mph at Φref ≈ 2.5).
Second, the cellular and helicoidal detonation
structures have been analyzed: typical sizes λ ∈
[3.0 mm, π · 76 ≈ 240 mm] ≈ [0.12 , 9.4 ] and
standard deviations λ ≈ 0.3 · λ, have been mea-
sured.
(4) The sensitivity to detonation has been kineti-
cally interpreted [2–4] by applying the theoret-
ical “0D” model further designed by ZND (Zel’-
dovitch, von Neumann, and Döring [10–12]).
The ignition delays τ sim required by this calcu-
lation have been simulated:
• using S ENKIN with the modified mechanism;
• considering the von Neumann parameters T vN
and P vN , i.e., the average of the extremely het-
erogeneous thermodynamical states behind the
shock front.
1.2. Interest in using Arrhenius-type correlations for
high-temperature kinetic studies
As underlined by Davidson and Hanson [13], de-
veloping correlations for experimental ignition delays
is very useful, because:
(1) Some modelers require them for their engine pro-
grams or reactive flow codes, rather than using
full or reduced kinetic models to describe the
chemical processes.
(2) These relations can be helpful for experimental
work, by reducing the number of data needed to
fully examine the ignition behavior of a particu-
lar fuel.
(3) These expressions allow comparison of ignition
delays, from studies that might have been con-
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
ducted with various reaction conditions and term
definitions.
In addition, some kinetic properties of the det-
onation can be understood, analyzing the induction
delays τ sim , as well as the activation temperatures
θ a, sim deduced from them. Of particular interest is
the sensitivity of these parameters to:
• the mixture composition: the equivalence ratio Φ
and the inert fraction X Ar ;
• the average thermodynamic state in the detona-
tion wave: the von Neumann parameters T vN and
P vN ;
• the mean particle velocity uvN , in the referential
related to the shock front.
Because the number of elementary reactions in-
creases considerably with the length of the alkyl
chain, the combustion mechanism quickly becomes
uneasy to handle for:
• complex fuels such as gasoline, kerosene, diesel
(and the equivalent biofuels);
• reactive surrogates (and even isolated “heavy
molecules”) representative of these practical
compositions.
This is why, despite increasing computing power,
the simulation of the delays τ sim using C HEMKIN or
other tools may continue to consume much time in
many cases. Therefore, it can be interesting to use the
traditional semi-empirical correlation of ignition de-
lays:
 
θa
τcor = A · [Fuel]α · [O2 ]β · [Inert]γ · exp . (1)
T species considered as:
This simple relation, inspired by the Arrhenius equa-
tion [14], and Semenov’s considerations about the
thermal autoignition process [15], was first published
by Lifshitz et al. [16] and widely used since then. Its
success comes from the ability to estimate the em-
pirical delays τ exp , quickly (from 105 to 108 faster
than a standard mechanism) with a convenient accu-
racy (provided that the investigated initial conditions
do not differ much from the ones used to establish the
correlation).
To properly use this “0D” concept, it matters that
the reactions in the neighborhood do not really change
the chemical development, which should only depend
on the initial conditions, as if the chemistry scheme
has been “frozen” since its onset. Such a restriction
is not problematic in studying the kinetics of the
gas-phase detonation. The involved reactions are so
fast that the impact of convection on the local induc-
tion process can be reasonably neglected: despite the
383
strong flow turbulence behind the shock front, there
is nearly no time for movement of active species in-
side the gas, neither heat losses to the walls. However,
extrapolation of such a relationship is needed to esti-
mate ignition delays in detonation waves.
These simplifications explain why Auffret et al.
[17], for instance, employed this formalism to deter-
mine the induction distances i = τi · uvN , typical of
the detonations of C2 H2 /O2 mixtures. This calcula-
tion, based on the ZND model, has enabled them:
(1) to evaluate the average self-sustained detonation
cell width as λ ≈ 29·i , in agreement with West-
brook et al. [18];
(2) to predict the sensitivity to detonation, because
the initiation energy of spherical detonation is
roughly proportional to λ3 (according to Zel’-
dovitch et al. [19]) and thus to τi3 .
1.3. Place of the proposed formalism among existing
reduction processes
In chemical kinetics, the use of polynomials to
speed up the simulations is not new: Turányi [20,21]
has already applied the repromodel. This mathemat-
ical tool is intended to reproduce the output of the
complex model with high accuracy and high speed.
The creation of such a model requires extra effort, but
the savings in computer time can be tremendous.
In the case of the kinetic studies dealing with
combustion or atmospheric pollution carried out by
Turányi and by Tomlin et al. [22], the mechanism is
simplified according to a three-step protocol:
(1) Ordering, for the investigated conditions, of the
• “redundant” and so likely to be removed from
the mechanism during a preliminary simplifi-
cation step;
• “important” and grouped in submodels, there-
after mathematically analyzed;
• “necessary” and employed as parameters for
the repromodel.
(2) Design of high-order orthonormal polynomials
intended to reproduce the characteristic varia-
tions of the groups composed of the secondary
variables, in function of the main parameters.
(3) Simplification of these polynomials by the re-
moval of the noninfluential terms (selected
among hundreds—or even thousands—of coef-
ficients).
Consequently, the repromodel applied to chemi-
cal kinetics by Turányi and by Tomlin et al. [20–22],
takes as inputs:
384 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
• the concentrations of the species considered as
necessary;
• the global varying parameters such as tempera-
ture (or light intensity, in the case of photochem-
ical reactions).
As outputs, this polynomial provides the variations of
the concentrations of the necessary species.
Turányi [21] highlights the improvements of his
method by comparing its performances with those of
the original mechanism and of other reduction pro-
cesses which are:
• “purely mathematical,” like ILDM (intrinsic low-
dimensional manifold);
• “chemico-mathematic,” like QSSA (quasi-steady
state approximation) and CSP (computational
singular disturbance).
Turányi takes into account a list of criteria, among
which five will be employed in this article to evalu-
ate the performances of the new correlation:
(1) the human efforts required to prepare the simpli-
fied model;
(2) the applicability field of the model and its im-
portance compared to the domain covered by the
database;
(3) the gain in computing time (typically from 102 to
104 for Turányi’s work);
(4) the precision of the results (less than 1% of devi-
ation for the repromodel);
(5) the degree of understanding of the chemical phe-
nomena as described by the model.
The latter notion is generally illustrated by two ex-
treme cases:
• the behavior model (trivially called black box),
which is easy and quick to handle, but in coun-
terpart provides little (or even no) accessible
useful information: for example, a pure “math-
ematical model” difficult to safely extrapolate,
like an Arrhenius correlation with a few coeffi-
cients;
• the knowledge model, which offers deep in-
sight, but requires time to be used and know-how
to be properly handled: for example, a well-
documented detailed mechanism using more or
less complex formalisms such as those developed
by Lindemann et al. [23] and then extended by
Troe [24].
This work, related to the combustion behind shock
waves and in detonation waves, retains the goals of
the mathematical notion of repromodeling. However,
the objectives here are much more limited than those
of Turányi and Tomlin et al.: the aim of our behavior
model is to estimate the ignition delay from global
parameters.
For these high-temperature processes involving a
chemical reactivity likely to develop in the microsec-
ond range, this duration is indeed meaningful, be-
cause of the actually little time left for mass and heat
transfer.
In addition, ignition delays are experimentally ac-
cessible, thanks to unambiguous measurements based
on:
• the pressure registration (in the case of concen-
trated mixtures);
• the emission spectroscopy (in most cases), de-
scribing the relative evolution of the concentra-
tions of excited species (such as OH∗ or CH∗ )
relaxing by fluorescence;
• the absorption spectroscopy (sometimes), re-
lated to the concentration of intermediates at the
ground state, likely to be excited by lasers;
• the chromatography and the spectrometry (very
rarely, because of the little time left for analysis).
Finally, the ignition process is quite simple to
model, because of the quasi-simultaneous and large
variations of all the kinetic parameters during the ex-
ponential growth of the radical pool generated by the
energy release consecutive to the induction stage.
1.4. Objectives and plan of the article
This article shows how the semi-empirical correla-
tions intended to fit n-heptane ignition delays can be
reformulated into polynomials with 3N coefficients,
when N ∈ [1, 4] represents the number of adjustable
kinetic parameters likely to be simultaneously chosen
among T , P , X Ar , and Φ. These behavior models do
not aim at correlating the ignition delays measured
with a shock tube (as for the majority of the experi-
mental studies), but are aimed at those calculated us-
ing a validated detailed chemical kinetic mechanism,
in order to provide a database broad and diversified
enough for a discussion.
It will be shown that despite the high computa-
tional speed-up aimed at the performances of the tra-
ditional correlations, the deviations between the pre-
dictions τ sim and their fits τ cor are maintained neg-
ligible compared to the uncertainties of the original
model. So, the prediction quality seems preserved by
this new formalism.
Another advantage of this method is its applica-
bility to a wide range of temperatures, pressures, di-
lutions in argon, and equivalence ratios, comparable
with the validity domain of the detailed mechanism.
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
To obtain such results, this article:
(1) analyzes the traditional Arrhenius-type correla-
tions (Section 2);
(2) confronts these classical expressions with the de-
tailed model (Section 3);
(3) exposes how the new formalism is built (Ap-
pendix A);
(4) characterizes its performance (Appendix A): re-
production quality and computational speed;
(5) exhibits the evolutions of the ignition delays τ
(Section 4), then the activation temperatures θ a
(Section 5), predicted by the mechanism for high
temperatures, as illustrations of the potentialities
of the proposed formalism.
The advanced correlations are intended to enable
quick modeling of the kinetic properties of the au-
toignition of n-heptane-based mixtures, as well as
their sensitivity to detonation. So, the tool here pro-
posed has been developed for studies dealing with:
• interpretation of the detonation cellular structure
by means of the “0D” ZND model;
• analysis of the predictions of a detailed mecha-
nism;
• coupling of chemical kinetics and fluid mechan-
ics in multidimensional simulations.
2. Analysis of Arrhenius-type formalism in the
case of n-heptane autoignition
2.1. Characteristics of traditional semi-empirical
correlations
In the case of the combustion of n-heptane/oxygen/
argon mixtures, the ignition delay τ can be written as
the inverse of a fictive global speed law:
 
α β γ θa
τcor = A · [C7 H16 ] · [O2 ] · [Ar] · exp , (2)
T
derived from Eq. (1), with
• the pre-exponential factor A (here: µs
m3 · (α+β+γ ) mol−(α+β+γ ) );
• the activation temperature θa = Ea /R (K), with
the activation energy E a (J mol−1 );
• the exponents α, β, and γ (dimensionless), re-
spectively related to the concentrations of the
fuel n-heptane, oxygen, and the inert argon; co-
efficients comparable to the partial orders of a
global combustion rate law (up to sign).
This expression provides the evolution of the ex-
perimental delay τ exp , with a fairly good approxima-
tion. For n-heptane, ln[τexp ] (i.e., the order of magni-
385
tude of τ exp ) grows in a quasi-linear way, with T −1 ,
for the high-temperature range, i.e., for temperatures
above:
• 850 K ≈ 575 ◦ C ≈ 1070 ◦ F,
at 500 kPa = 5 bar ≈ 70 psi;
• 900 K ≈ 625 ◦ C ≈ 1160 ◦ F,
at 1.4 MPa = 14 bar ≈ 200 psi;
• 1000 K ≈ 725 ◦ C ≈ 1340 ◦ F,
at 4.0 MPa = 40 bar ≈ 580 psi.
These critical values, corresponding to the border
with the NTC (negative temperature coefficient) do-
main, are deduced from the investigations carried out
by Chevalier et al. [25].
The interpolation of the traditional semi-empirical
correlations (expressed as Eqs. (1) and (2)), within
their validity domain, gives good results: the ratio
between the ignition delays τ cor and τ exp generally
remains between 0.5 and 2. Despite this uncertainty
factor lower than 2, it is often hazardous to extrapo-
late these expressions far from their validity ranges.
This feature explains why the kineticists prefer to use
mechanisms (detailed, reduced, or even skeletal) that
keep the advantage of knowledge models, with phys-
ical concepts enabling safer extrapolations.
2.2. Reformulation of the traditional semi-empirical
correlations
To highlight the influential physicochemical fac-
tors, Eq. (2) can be modified by clarifying the depen-
dence rules between the delay τ cor and:
• the thermodynamic state (T , P );
• the composition, usually expressed by means of:
– the molar fractions of each component:
X C7 H16 , X O2 , and X Ar ;
– the equivalence ratio Φ and the inert fraction
X Ar .
By assuming that the ideal gas law is valid for
pressures significantly lower than 10 MPa = 100
bar ≈ 1450 psi, the concentration [Y] of each species
is easily calculated for a given T , from its partial pres-
sure P Y (bar). The latter can be expressed in terms of
the fraction X Y and the total pressure P , according to
PY XY · P
[Y] = = (3)
R·T R·T
(R = gas constant), which, combined with Eq. (2),
implies
A α β γ
τcor = · XC 7 H16
· XO · XAr
R (α+β+γ ) 2
   (α+β+γ )
θa P
× exp · . (4)
T T
386 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408

Table 1
Experimental conditions and ignition delays for high-temperature combustions of n-C7 H16 /O2 /Ar mixtures in shock tubes
References X Heptane X Argon Equivalence Pressure Temperature Delay
(mol%) (mol%) ratio Φ (–) P5 (bar) T5 (K) τ (µs)
Vermeer et al. [26] 2.5 70 1.0 1.3 to 4.1 1270 to 1580 13 to 530
Coats et al. [27] 0.09 to 0.7 95 to 98 0.5 to 4.0 1.1 to 2.0 1300 to 2000 30 to 1250
Burcat et al. [28] 0.5 to 3.0 64 to 88.5 0.5 to 2.0 2.0 to 11.8 1135 to 1660 12 to 647
Colket et al. [29] 0.2 95.6 and 97.7 0.5 and 1.0 4.1 to 7.8 1225 to 1430 88 to 844
Horning et al. [30] 0.2 to 1.8 78 to 97.6 0.5 to 2.0 1.1 to 5.7 1330 to 1680 86 to 490
Imbert et al. [1] 0.08 to 1.0 88.0 to 99.0 0.5 to 1.5 2.5 to 7.2 1290 to 1600 37 to 680
Smith et al. [31] 0.4 90.8 to 97.4 0.5 to 2.0 1.0 to 2.0 1150 to 1650 40 to 1000

P MMixture
This expression of τ cor exhibits the “pressure coeffi- ρ= · , (10b)
cient” p, defined as the global order (i.e., the sum of T R
the partial orders of every species): where M Mixture represents the average molar mass of
the mixture.
p = (α + β + γ ). (5)
τ cor can be also linked to Φ, since in the case of 2.3. Analysis of the traditional semi-empirical
{C7 H16 /O2 } mixtures
correlations
XC7 H16 /XO2
Φ= ⇔ (6a)
1/11 2.3.1. Expressions published for n-heptane
XC7 H16 Φ autoignition
= , (6b)
X O2 11 Table 1 lists in the case of n-heptane:

1 − XAr = XReac = XO2 + XC7 H16 • the shock tube ignition delays τ exp , already pub-
 
XC7 H16 lished [1,26–31];
= XO2 · 1 + • the experimental conditions used for these high-
X O2
  temperature investigations.
Φ
= XO 2 · 1 + , (7)
11
Table 2 exposes the semi-empirical correlations de-
and therefore duced from these measurements and reformulated to
 −(α+β) facilitate their analysis and comparison.
A α · 1+ Φ
τcor = · Φ
11α · R (α+β+γ ) 11
γ 2.3.2. Role of the temperature T
XAr
× As demonstrated by Arrhenius, temperature plays
(1 − XAr )−(α+β) a major role in chemical kinetics. Due to the break-
   (α+β+γ ) ing of bonds, during the initiation process, the slope
θa P
× exp · . (8) of the quasi-linear relation ln(τexp ) = f (T −1 ), re-
T T
lated to the induction time, remains generally very
This expression of τ cor exhibits the “implicit coeffi- high. Here, the deviations between the activation tem-
cient related to dilution.” This parameter, used as an peratures θa ∈ [17.8 × 103 K, 35.2 × 103 K] (activa-
exponent for (1 − XAr ), can be defined as the opposite tion energies Ea ∈ [148 kJ mol−1 , 293 kJ mol−1 ] ≈
of the sum of the partial orders linked to the reactants: [35.3 kcal mol−1 , 70.0 kcal mol−1 ]), measured by all
the authors have been explained [1]:
x = −(α + β). (9)
For CFD (computational fluid dynamics), density • by the difference in amplitude (from 200 K (or
ρ can be a more convenient parameter, although it ◦ C), i.e., 360 ◦ F, to 700 K, i.e., 1260 ◦ F), and po-
cannot be directly evaluated through experiments in sition (maximum between 1430 K ≈ 1160 ◦ C ≈
shock tubes. Small adaptations of Eq. (4) (and follow- 2110 ◦ F and 2000 K ≈ 1730 ◦ C ≈ 3140 ◦ F) of
ing expressions directly based on it) are then needed. the investigated temperature ranges;
Practically, it is enough to replace P /T by ρ, using • by the diversity of the dilution importance from
P R less than 70% to more than 99% of the mixture
=ρ· ⇔ (10a) filled with argon.
T MMixture
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408 387

Table 2
Expression of the semi-empirical correlations τ cor (µs) (established from the delays τ exp measured for the conditions described
in Table 1) as a function of temperature T (K), pressure P (bar), and the concentrations [Mixture], [C7 H16 ], [O2 ], and [Ar]
(mol m−3 )
References Semi-empirical correlations x p
 
Vermeer et al. [26] τcor = 7.34 × 10−5 · [Mixture]−0.86 · exp 23T340 +0.86 −0.86
 
Coats et al. [27] τcor ∝ [C7 H16 ]+1.42 · exp 35T300 – –
 
Burcat et al. [28] τcor = 2.0 × 10−4 · [C7 H16 ]+0.2 · [O2 ]−1.1 · [Ar]+0.6 · exp 17T765 +0.9 −0.3
 
Colket et al. [29] τcor = 4.26 × 10−4 · [C7 H16 ]+0.4 · [O2 ]−1.2 · [Ar]0 · exp 20T211 +0.8 −0.8
 
Horning et al. [30] τcor = 2.73 × 10−4 · [C7 H16 ]+0.95 · [O2 ]−1.58 · [Ar]0 · exp 22T647 +0.63 −0.63
 
Imbert et al. [1] τcor = 1.21 × 10−5 · [C7 H16 ]+0.92 · [O2 ]−1.41 · [Ar]+0.09 · exp 26T922 +0.49 −0.40
 
Smith et al. [31] τcor = 10(−3.30±0.04) · (1.013 · P )(−0.468±0.043) · exp 20 650±139
T – −0.468
Evaluation of the “implicit coefficient of dilution” x = −(α + β) and of the “pressure coefficient” p = (α + β + γ ), using the
“partial orders” α, β, and γ (dimensionless), respectively related to [C7 H16 ], [O2 ], and [Ar].

2.3.3. Role of the pressure P
Generally speaking, the reactivity grows with
pressure, which implies that the sensitivity to pres-
sure factor p = (α + β + γ ) remains negative (here:
p ∈ [−0.83, −0.3]).
Several kinetic approaches enable the qualitative
understanding of this power-type dependence, and
notably:
• the “fall-off” model developed by Lindemann et
al. [23], which explains the change in the molec-
ularity (“number of reactants”) of the elementary
reactions with pressure;
• the RRKM theory [32], which provides simple
estimates of the unimolecular reaction rates, from
a few characteristics of the potential energy sur-
face.
In accordance with these models:
(1) The elementary reaction AB (+M) → A + B
(+M) proceeds according to the following global
scheme, composed of three steps:
• AB + M → AB∗ + M
(k1 ): activation of the reactant AB by the col-
lision partner M;
• AB∗ + M → AB + M
(k−1 ): deactivation (also by collision) of the
reaction intermediate AB∗ , vibrationally ex-
cited;
• AB∗ → A + B
(k2 ): dissociation of AB∗ into products A
and B.
(2) The speed of this “so-called elementary reac-
tion,” assuming QSSA for AB∗ , is
 
d[AB] k1 · k2 · [M]
v=− = · [AB]
dt k−1 · [M] + k2
⎧  k1 ·k2 
⎪
⎪ · [AB] (molecularity 1),
⎪
⎨ −1
k
at high pressure,
≈
⎪
⎪
⎩ (k1 · [M]) · [AB] (molecularity 2),
⎪
at low pressure.
(11)
As concentrations of the main active species dur-
ing the autoignition process are often low, the tran-
sition pressures, although evolving with temperature,
are generally worth about several bars. Because these
pressures are much higher than the ones investigated
here, the apparent molecularities of the elementary re-
actions involved during induction often exceed unity.
The exponent p, bounded to the “global” reaction,
results from the overall combination of each molec-
ularity, weighted by the importance of the related el-
ementary reaction. Consequently, its determination is
complex. For example, it may depend on the compe-
tition between two elementary reactions, one second
order and another third order, which are respectively
especially active at low and high pressures.
Actually, the pseudo-order of the “global” reaction
is given by (1 − p): for example, p = 0 would corre-
spond to the case of the strictly unimolecular reaction,
for which the ignition delay does not depend on pres-
sure. Here (1 − p) is intermediary between 1 and 2.
This value implies that the reactions involved by the
autoignition process (mainly the initiation stage of the
chain reaction, which is combustion) are not really
unimolecular due to:
(1) the importance of the collision partner, as de-
scribed by the Lindemann “fall-off” model;
(2) the presence of reactions involving two or more
reactants, that is, reactions other than decompo-
sition, β scission, isomerization, etc.
388 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408

2.3.4. Role of the inert or reactive fraction XAr and Table 3

XReac Experimental validation range associated with the Curran et
Concerning the dilution impact, the correlations al. original mechanism [6,7] and conditions for simulation
(Table 2) confirm the intuition: τ cor increases with using the version modified by Imbert et al. [1]
X Ar , all other parameters being equal: Parameter Validation Conditions
range of use
γ  0 and x = −(α + β) > 0 ⇒ Pressure P (bar) 1 to 42 0.1 to 10
γ Temperature T (K) 550 to 1700 1300 to 1900
XAr
τcor ∝ strictly grows with XAr . Equivalence ratio Φ (–) 0.3 to 1.5 0.25 to 4.0
(1 − XAr )x Argon fraction X Ar (–) 0.70 to 0.99 0 to 0.70
This dependence type shows that argon addition in- Reactive fraction X Reac (–) 0.01 to 0.30 0.30 to 1.00
creases τ cor :
2.4. “Linearization” of Arrhenius-type expressions
• explicitly, through the coefficient γ of [Ar]: tak-
ing into account the singular effect of argon, as To continue the calculation development, the
a special collision partner to deactivate the in- semi-empirical correlation (Eq. (8)) is linearized by
termediate reactants (to be noted that γ is often applying a logarithm transform:
neglected and imposed on zero, as seen in Ta-
ble 2); lg(τcor ) = Lτref + f (Φ) + γ · lg(XAr )
• implicitly, with the coefficients α and β related θa
to the concentrations [C7 H16 ] and [O2 ]: mani- − x · lg(1 − XAr ) +
T
festation, through the so-called “implicit dilution − p · lg(T ) + p · lg(P ) (12)
coefficient” x = −(α + β), of the rarefaction of
these two reactants. with:

A
• Lτref = lg( α (α+β+γ
2.3.5. Role of the proportion between reactants 11 ·R ) ), later directly evalu-
(equivalence ratio Φ) ated, and assumed as a constant;
• f (Φ) = α · lg(Φ) + x · lg(1 + 11 Φ ) complex de-
The correlations (Table 2) show a dependence of
τ cor : pendence, reformulated thereafter to keep the lin-
earity;
• slightly increasing with [C7 H16 ], since α  0.2; • γ = 0: assumption often used (Table 2), and here
• definitely decreasing with [O2 ], since β  −1.1; intended to avoid a discontinuity for the undi-
• increasing with Φ, and varying in luted mixtures (practically for very low values of
XAr ∈ [0, 0.7]).
 
Φ −(α+β)
Φα · 1 + (deduced from Eq. (8))
11
3. Confrontation between Arrhenius formalism
with: −(α + β) = x  0.49. and mechanism predictions

It is worth noting that n-heptane—though reactive
—inhibits its own ignition (α > 0), contrary to oxy-
gen, which definitely promotes it (β < 1). This fea-
ture is usual with alkanes, but not general for all the
fuels (for example, monomethylhydrazine CH3 N2 H3 ,
studied by Catoire [33]), depending on their chemical
natures. For high-temperature combustion, this be-
havior especially results from a competition between
fuel and oxygen, for reactions with ◦ H atoms, accord-
ing to:
• RH + H◦  R◦ + H2 : metathesis generating a
radical R◦ heavier than ◦ H, thus less reactive;
• O2 + H◦  ◦ OH + O: chain branching, leading
to the “exponential” growth of the number of re-
action intermediates, and causing the very quick
energy release during an explosion.
3.1. General information concerning analysis of
simulated delays τsim
The program S ENKIN (C HEMKIN III package) has
enabled the prediction of ignition delays τ sim , defined
as the time interval between the onset of the shock
wave and the maximum of dT /dt curve: the temper-
ature rise inflection generally occurs simultaneously
with the emission peak related to the excited radical
◦ OH∗ .
These delays τ sim have been evaluated using the
Curran et al. mechanism [6,7], somewhat modified
by Imbert et al. [1]. The conditions employed here to
model the ignition have slightly surpassed the experi-
mental validation range (Table 3), as is often the case
when a mechanism is used, especially with regard to
the high temperatures.
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408 389

Basically for the calculation, the combustion has

been assumed to develop in a constant volume, with-
out heat losses, since:

• the shock tube is a closed reactor;

• the ignition delays are too short, to allow:
– the pressure waves to relax far from the induc-
tion zone;
– the gas core to be cooled by an exchange with
the boundary layers bordering the wall.

With a Pentium III running at 500 MHz, about 15 min

of calculations were required for each ignition delay.
Figs. 1–4 illustrate the evolution of the delays with
the parameters T , P , Φ, and XReac = 1 − XAr . The
performances of the various relationships presented
in Table 1 will be quantified by the standard devi-
ation τ cor , between the simulated ignition delays Fig. 1. Evolution of the ignition delays (P for the reference
τ sim , used as references, and their fits τ cor (defini- simulated value τ sim ; dashed line for the correlation τ cor )
tion expressed by Eqs. (A.17) and (A.18) in Appendix with the temperature T and its inverse T −1 (normal–log
A.4). scale), around T ref = 1700 K. Arrhenius diagram estab-
All the parameters presented in this section (the lished for the mixture n-C7 H16 /O2 (Φref = 1) at P ref = 100
kPa. Reference points obtained with the modified mecha-
activation energies θ a, sim , the pressure coefficients
nism (Imbert et al. [1]).
p, the implicit dilution coefficients x, and the partial
pseudo-orders α related to n-heptane) will provide a
3.2. Evolution of τsim with T
frozen image of the predictions of the detailed mecha-
nism for a particular condition (here, the one arbitrar-
Clearly, the temperature remains the parameter
ily chosen as a reference).
with the most influence on the ignition delay: as illus-
It is difficult to deeply interpret the differences and
trated in Fig. 1, τ sim shortens by about a factor 140
the similarities between the simulated and the semi- (from 280 µs down to 2.0 µs) when T increases by
empirical values. This work, close to the comparison 45% (from 1300 K up to 1900 K).
between various Arrhenius-type correlations related The dashed line (inspired by the original Arrhe-
to the same fuel, is beyond the scope of this study. nius rate law) correctly fits τ sim , although τcor > τref
At this stage of the kinetic study, it is only possible in the center of the graphic (line above the triangles)
to list, as did Davidson and Hanson [13], the possible and τcor < τref at its ends (line below the triangles):
origins of the disagreements between semi-empirical
 
τcor T
correlations: = exp −11.6 · 1 − ref
6.13 T

 
• the use for conditions outside the validity do- 3 1 1
= exp 19.7 × 10 · −
main; T Tref
• the differences in the definition of the ignition de- ⇒ τcor = 5.0%. (13)
lays (especially the choice of the time markers);
• the errors in the experimental methods (partic- The mathematical use of a second-order polynomial
in T −1 enables better reproduction of the slight con-
ularly the limitations inherent to the shock tube
vexity, source of the deviation τ cor between the
and to the diagnostics).
simulated delays τ sim and their fit τ cor :
   
In addition, it must be kept in mind that the discrep- τcor 1 1
ln = 18.9 × 103 · −
ancies with the measured ignition delays τ exp are im- 6.01 T Tref
portant:  
1 1 2
+ 7.20 × 106 · −
• at least 25%, for the duration τ sim , simulated by T Tref
the modified detailed mechanism; ⇒ τcor = 0.7%. (14)
• typically a factor 2, for the time τ cor , calculated It is also possible to use the modified Arrhenius-type
using the semi-empirical correlations. law by putting an exponent on T (here, the value is
390 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408

directly deduced from the best fit):

 
 
τcor T 11.5 1 1
= · exp 38.3 × 103 · −
6.01 Tref T Tref
⇒ τcor = 0.5%. (15)

The formalism of Eq. (15) is inspired by expression of

the elementary rate constants. On one hand, for a data-
processing complexity comparable with the second-
order polynomial fit (Eq. (14)) in T −1 , this expres-
sion reduces the deviation τ cor . On the other hand,
correlation (15) masks θ a, cor , which now requires the
intermediate calculation of at least two τ cor delays to
be evaluated. Despite this disadvantage, this type of
formalism will be selected to develop the new corre-
lations.
The apparent activation temperatures θ a, sim , es-
tablished by the linear regression ln(τcor ) = f (T −1 )
around T ref , remain almost the same for Eqs. (13)–
(15), respectively 19.7 × 103 K, 18.9 × 103 K, and
18.8 × 103 K, corresponding to activation energies
E a, sim about 160 kJ mol−1 or 38 kcal mol−1 . This
property shows that the slight convexity of ln(τsim ) =
f (T −1 ), although not easily visible in Fig. 1, weakly
influences the simulated apparent activation temper-
atures θ a, sim . Moreover, they remain close to the
semi-empirical values, deduced from n-heptane cor-
 2
relations (Table 2):
• θa, cor ≈ 17.8 × 103 K, for Burcat et al. [28];
• θa, cor ≈ 20.2 × 103 K, for Colket and Spadaccini
[29];
• θa, cor ≈ 20.7 × 103 K, for Smith et al. [31].
3.3. Evolution of τsim with P
Pressure has a smaller influence on the ignition
delays than temperature: whereas the range covered
by P extends much more (in logarithmic scale) than
the one related to T , the impact on τ sim remains of
the same order of magnitude in both cases: as illus-
trated in Fig. 2, τ sim only shortens by about a factor
30 (from 38 µs down to 1.2 µs) when P increases by
a factor 100 (from 100 kPa up to 10 MPa).
Due to the quasi-linear relationship between P
and τ sim , for a log–log scale, the dependence seems
to be of power type
Fig. 2. Evolution of the ignition delays (P for the reference
simulated value τ sim ; dashed line for the correlation τ cor )
with the pressure P (log–log scale), around P ref = 100 kPa,
for the mixture n-C7 H16 /O2 (Φref = 1) at T ref = 1700 K.
Reference points obtained with the modified mechanism
(Imbert et al. [1]).
   
τcor P
lg = −0.763 · lg
5.94 Pref
P
+ 0.052 · lg
Pref
⇒ τcor = 0.1%. (17)
The coefficients psim ≈ −0.762 exhibited by Eqs.
(16) and (17) remain very close to the sensitivity fac-
tor to the pressure deduced from the semi-empirical
correlations (Table 2): pcor ≈ −0.8 from Colket and
Spadaccini [29], for example.
3.4. Evolution of τsim with XAr and XReac
The mixture dilution has also a secondary influ-
ence on the ignition delays: as illustrated in Fig. 3,
τ sim does not increase more than by a factor 10
(from 5.9 µs up to 55 µs), when the reactive fraction
XReac = XC7 H16 + XO2 = 1 − XAr decreases by a
factor 100 (from 1 down to 0.01).
The quasi-linear relationship between X Reac and
τ sim , for a log–log scale, leads to:

     
τcor P −0.762 τcor XReac −0.456 1 − XAr −0.456
= ⇒ τcor = 6.8%. (16) = =
6.25 Pref 6.15 1 1 − XAr,ref
⇒ τcor = 7.2%. (18)
The use of a second-order polynomial for the consid-
ered scale here enables a better reproduction of the The use of a second-order polynomial reduces the dis-
convexity with: crepancy:
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
Fig. 3. Evolution of the ignition delays (P for the reference
simulated value τ sim ; dashed line for the correlation τ cor )
with the fraction of the reactant X Reac (log–log scale) and
of the dilutant X Ar , for the mixture n-C7 H16 /O2 /Ar (Φref =
1) at T ref = 1700 K and P ref = 100 kPa. Reference points
obtained with the modified mechanism (Imbert et al. [1]).
   
τcor 1 − XAr
lg = −0.527 · lg
5.96 1
  (4) to carry out this temperature rise by still generat-
1 − XAr 2
− 0.044 · lg
1 the energy provided by the shock is then in ma-
⇒ τcor = 1.2%. (19)
These results are good with regard to the impor-
tance of the dilution range (2 orders of magnitude for
XReac ∈ [0.01, 1]). Consequently, the presence of the
γ
multiplicative term XAr in Eqs. (4) and (8) (which
causes continuity troubles through the logarithmic ex-
pression for XAr = 0) does not seem necessary to
correct the inflection of ln(τsim ) = f [ln(XAr )]. So,
“the partial order” γ , which exhibits the explicit influ-
ence of argon (Section 2.3.4), can be set to zero with-
out problem. As illustrated in Table 2, this is done in
the majority of the semi-empirical correlations (γ = 0
γ
implies XAr = 1, whatever the values of XAr ∈ [0, 1]
and XReac = 1 − XAr ).
Consequently, only the implicit kinetic effect (re-
lated to the decrease of the reactant concentrations)
plays a role. The absolute values of the exponents
x sim , −0.456 and −0.527 (slopes of τcor = f (XReac )
for XReac = 0, according to a log–log scale), can
be compared to the implicit dilution coefficients de-
duced from the semi-empirical correlations (Table 2):
xcor = 0.49 for Imbert et al. [1], for instance.
In addition, the minor impact on kinetics of the di-
lution (in comparison to the temperature one), a pos-
teriori validates the measurement protocol of the
shock tube ignition delays τ exp (Table 1). As ex-
391
plained by Davidson and Hanson [13], as well as by
Brun [34], the use of a minimum amount of an inert
“bath gas” enables the experimentators:
(1) to significantly lower the reaction mass enthalpy
and thus to limit the risks of an accidental deto-
nation onset;
(2) to absorb the energy variations behind the shock
waves (effect of “heat sink”) and thus:
• to homogenize the thermodynamic state;
• to attenuate the impact of the stochastic distur-
bances, especially in the medium shocked by
the reflected wave, which is very sensitive to
the boundary layers’ perturbations left by the
incident wave passage;
(3) to study the global kinetics for high tempera-
ture, while keeping τexp ∈ [10 µs, 1 ms] observ-
able and realistic to study the detonation: the dif-
ference in the induction delay related to a pure
mixture is approximately only an order of mag-
nitude;
and in the special case of the use of a monoatomic
“bath gas” like argon (instead of the diatomic nitro-
gen, employed to simulate air):
ing a moderate shock (Mach number Ms ≈ 2.5):
jority distributed to the degree of freedom in
translation, and only a small part is lost in the lev-
els of vibration and rotation present in the poly-
atomic reactants;
(5) to limit the influence of the vibrational relaxation
in the carrier gas and so to decrease the duration
required to reach the thermodynamic equilibrium
behind the shock waves;
(6) to minimize the bifurcation of the reflected shock
wave during its passage inside the boundary lay-
ers (generated near the wall by the previous pas-
sage of the incidental shock), consequence of the
fifth item.
On the other hand, these experiments are carried
out under conditions relatively far from those of prac-
tical combustion devices (engines or turbines):
• air contains only 79% of inert rather than 98%
(or even more);
• for the same inert fraction and energy release,
the high isentropic coefficient of argon (1.67 for
this monoatomic gas, greater than the diatomic
nitrogen one: from 1.4 at 300 K down to 1.3 at
2000 K) results in large variations of the mixture
temperature during the induction process, and so
possibly in a change of the ignition delay τ exp .
392 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
Fig. 4. Evolution of the ignition delays (P for the reference
simulated value τ sim ; dashed line for the correlation τ cor )
with the equivalence ratio Φ (log–log scale) for the mixture
n-C7 H16 /O2 at T ref = 1700 K and P ref = 100 kPa. Refer-
ence points obtained with the modified mechanism (Imbert
et al. [1]). Legend for the correlations extrapolated beyond
their validity range: long dashed line, decreasing with Φ, for
the very lean mixture; short dashed parabola, for the fairly
lean mixture; long dashed line, increasing with Φ, for the
rich mixture.
Consequently, disagreements between predictions of
mechanisms validated with mixtures very diluted in
argon and direct measurements with air are often ob-
served.
To conclude this issue, if the model correctly re-
produces the evolution of the ignition delays with
temperature, it can have difficulties making the same
with less influential kinetic parameters (such as di-
lution), due to the choice of the experimental condi-
tions.
3.5. Evolution of τsim with Φ
3.5.1. General
The equivalence ratio has a secondary influence on
the ignition delays: as illustrated in Fig. 4, τ sim does
not vary by more than a factor 10 (at most between
2.6 and 26 µs), when Φ evolves by a factor 80 inside
[0.05, 4.0] range intended to cover the flammability
domain of n-C7 H16 /O2 .
Certainly due to the complexity of the reaction
pathway, the simulated evolution cannot be repro-
duced in this whole area by the semi-empirical cor-
relations: the part of Eq. (8), restricted to the depen-
dence versus Φ varies as
 
According to the n-heptane detailed oxidation mech-
anism (Fig. 4), the evolution of τ sim with Φ can be
described by three branches, thereafter qualified by:
• very lean: Φ  0.15;
• lean, up to stoichiometric: Φ ∈ [0.15, 1.0];
• rich: Φ > 1.0.
In agreement with the log–log scale, the associated
correlations are illustrated by:
• short dashed lines for the extreme zones (very
lean and rich mixtures);
• a long dashed parabola for the central transition
zone (fairly lean medium and stoichiometric).
These functions are extrapolated beyond their validity
domains to underline the discrepancy (reference τ sim
(P); correlation τ cor (– –)), which could generate er-
rors in the case of a bad division of the equivalence
ratio range.
To facilitate comparison between the semi-empir-
ical correlations and the mechanism predictions, only
the evolution of Φ α will be considered. Indeed, the
fractional part of Eq. (20) can be neglected, because:
• it always remains close to unity;
• it slowly and weakly varies for rich mixtures:
no more than 15% for Φ ∈ [1, 4] by supposing
α + β ≈ −xsim ≈ −0.5;
• it remains quasi-constant for lean mixtures: ap-
proximately (12/11)−0.5 ≈ 0.96 for Φ  1 
11.
3.5.2. Rich mixtures (Φ > 1.0)
For rich mixtures, n-heptane inhibiting effect pre-
vails, due to the important rerouting of ◦ H atoms,
from chain branching (an essential reaction for the
high temperature combustion). Due to this feature,
τ cor increases with Φ:
 
τcor Φ 1.08
= ⇒ τcor = 1.5%. (21)
5.93 Φref
This exponent αsim = 1.08 remains close to the par-
tial orders α cor , deduced from the semi-empirical cor-
relations (Table 2):
• αcor ≈ 0.95, for Horning et al. [30];
  α+β • αcor ≈ 0.92, for Imbert et al. [1].
τcor Φ α Φ Φ
= · 1 + ref 1+
τref Φref 11 11 3.5.3. Very lean mixtures (Φ  0.15)

α+β For very lean mixtures, the small presence of hep-
12
= Φα · . (20) tane:
11 + Φ
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408 393

• rarefies the collisions between oxidizing and • a parabola (traditional mean in mathematics):
reducing species (unfavorable kinetic contribu-  
τcor
tion); lg = 1.12 · lg(Φ) + 0.92 · lg(Φ)2
• limits the rerouting of ◦ H atoms (favorable fac- 5.86
tor). ⇒ τcor = 1.9%; (23)
• a higher order polynomial (for better agreement):
In this extreme case, due to the prevalence of the first  
effect, τ cor decreases with Φ: τcor
lg = 1.22 · lg(Φ) + 1.19 · lg(Φ)2
5.93
  + 0.20 · lg(Φ)3
τcor Φ −0.42
= ⇒ τcor = 0.7%. (22)
1.29 Φref ⇒ τcor = 0.9%. (24)

Here, n-heptane behaves like a promoter of its own
ignition and no longer like an inhibitor.
Incidentally, it is difficult to give much credit to
the prediction of delays τ sim reported for Φ  0.15,
due to:
• the use of the mechanism in a range where it
has not been validated by experiments (even if
one big advantage of this knowledge model is the
possibility to extrapolate quite safely);
• the great difficulty of defining ignition delays, us-
ing S ENKIN simulations:
– progressive and slow increase in temperature
and pressure without marked inflection;
– complex exploring of the time profile of the
◦ OH radical concentration, which is the only
means to define ignition delays for those very
lean conditions.
3.5.4. Lean and stoichiometric mixtures
(Φ ∈ [0.15, 1.0])
For the intermediate range of Φ, due to the previ-
ously mentioned evolutions of τsim = f (Φ), the re-
actions become the fastest, any other parameters (T ,
P , and X Ar ) are fixed. For the reference conditions
(Tref = 1700 K, Pref = 100 kPa), the minimum delay
τ sim, min is obtained for the optimal equivalence ratio
Φopt,τ ≈ 0.25. These lean conditions (actually quite
far from stoichiometry) correspond to a compromise
where n-heptane is:
• abundant enough, so that the reactive species can
frequently collide during the propagation stages;
• in low enough proportion that a large number of
◦ H atoms remain, despite their capture by alkyl
radicals issued from the alkane, during metathe-
sis reactions.
Since this zone corresponds to the local minimum
of τsim = f (Φ), it can be correlated in good approx-
imation by the “flattened” vicinity of the bottom re-
lated to:
The use of a complex polynomial requires more cal-
culations:
• to evaluate the correlation;
• to determine a database related to reference con-
ditions.
This constraint is not justified to study detonation ki-
netics, since the range to be reproduced is limited
to reactive explosive mixtures, and this is practically
quite close to stoichiometry.
A smart mathematical solution thus consists of:
• restricting the interpolation range only to the use-
ful zone: Φ ∈ [0.25, 1.0], for example;
• simply using a parabola (log–log scale):
 
τcor
lg = 1.17 · lg(Φ) + 0.99 · lg(Φ)2
5.91
⇒ τcor = 0.6%. (25)
The evolution of τ sim is correctly reproduced under
conditions of forced quasi-tangency between the cen-
tral parabola and the extreme line related to the rich
mixture. This connection condition between lean and
rich mixtures will be respected to establish the corre-
lations reported in Appendix A (Tables 4–7).
3.5.5. Conclusion about the impact of Φ on τsim
The power-type law in Φ α for τ cor seems well
adapted, where one of the reactants is clearly in ex-
cess:
• for rich mixtures, the exponent 1.08 borders the
partial order α linked to [C7 H16 ], deduced from
the semi-empirical correlations;
• for very lean mixtures (Φ  0.15  11), the ex-
ponent −0.42 should be directly related to α (ac-
cording to Eq. (20)), but in fact takes an opposite
sign.
Since the absolute value of −0.42 is small compared
to 1.08, the negative impact (caused by the lack of
394 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408

Table 4
Coefficients related to Eq. (A.19) reproducing the delays τ sim , with a deviation lower than 1.5%
τ ref, 1 (µs) a1 b1 10 · c1 d1 e1 100 · f1 g1 h1
5.9492 −9.8017 11.556 −7.7446 1.4355 −4.1649 5.1452 1.3880 −2.8054
Simulation related to the mixture (n-C7 H16 /O2 , X Ar = 0 and Φ = 1) initially at T ∈ [1500 K, 1900 K] and P ∈
[10 kPa, 1 MPa].

Table 5
Coefficients related to Eq. (A.20) reproducing the delays τ sim , with a deviation lower than 1.5%
τ ref, 2 (µs) a2 b2 10 · c2 d2 e2 100 · f2 g2 h2
5.9492 −9.7926 11.524 −7.6260 1.4388 −4.1716 5.1511 1.3880 −2.8022

10 · i2 j2 k2 1000 · l2 m2 n2 1000 · o2 p2 q2
−5.9470 3.8080 −8.9598 4.3591 −1.2543 3.2734 9.3907 3.2218 −7.2594

10 · r2 s2 t2 100 · u2 10 · v2 w2 100 · x2 y2 z2
−1.4835 −3.5744 9.6339 4.4238 6.9279 −1.9606 3.8142 6.8344 −15.878
Simulation related to the diluted mixture (n-C7 H16 /O2 /Ar, Φ = 1 and XAr ∈ [0, 0.7]) initially at T ∈ [1500 K, 1900 K] and
P ∈ [10 kPa, 1 MPa].

Table 6
Coefficients related to Eq. (A.21) reproducing the delays τ sim , with a deviation lower than 2.5%
τ ref, 3 (µs) a3 b3 10 · c3 d3 e3 100 · f3 g3 h3
5.9639 −9.5896 11.028 −7.6208 1.5059 −4.3281 5.0315 1.1765 −2.2888

i3 j3 k3 10 · l3 m3 n3 100 · o3 p3 q3
1.0947 12.368 28.016 −2.1004 −6.1010 15.874 −6.9263 3.7162 −8.9187
Simulation related to the rich mixture (n-C7 H16 /O2 , Φ ∈ [1.0, 4.0] and XAr = 0) initially at T ∈ [1500 K, 1900 K] and
P ∈ [10 kPa, 1 MPa].

Table 7
Coefficients related to Eq. (A.22) reproducing the delays τ sim , with a deviation lower than 3.5%
τ ref, 4 (µs) a4 b4 10 · c4 d4 e4 100 · f4 g4 h4
5.9594 −9.6144 11.092 −7.6220 1.4998 −4.3167 5.0400 1.1954 −2.3350
i4 j4 k4 10 · l4 m4 n4 10 · o4 p4 q4
1.1509 21.600 −53.524 −1.2920 −1.3344 6.2639 −1.0040 −3.5367 8.8039

10 · r4 s4 t4 10 · u4 v4 w4 100 · x4 y4 z4
9.4960 29.676 −65.913 −1.6400 −12.332 31.079 −7.0100 −5.5594 11.871
Simulation related to the lean mixture (n-C7 H16 /O2 , Φ ∈ [0.5, 1.0] and XAr = 0) initially at T ∈ [1500 K, 1900 K] and
P ∈ [10 kPa, 1 MPa].

heptane for very lean mixtures) seems less marked
than the positive one (resulting from its excess for rich
mixtures).
These temporary conclusions, dealing with very
lean mixtures, have only small practical meaning,
since these conditions:
• remain little explored during measurements of
delays τ exp , due to the proximity of the lower
explosion limit (for n-heptane, at ambient tem-
perature: XC7 H16 ≈ 1.05% and Φ ≈ 0.05);
• have little interest for practical kinetic studies re-
lated to the combustion in engines or turbines (in
both the deflagration and the detonation modes).
3.6. Temporary conclusion and formulation of
significant reduced variables
This paragraph describes the relevance of trans-
posing the formalism deduced from semi-empirical
correlations to detailed mechanism predictions. Ex-
cept for the dependence (τsim | Φ) related to lean
mixtures, the agreement (traditional semi-empirical
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408 395

correlation | detailed mechanism) is good with regard τ sim and of the activation temperatures θ a, sim for n-
to: heptane combustion at high temperature is based on
the use of polynomial correlations such as
• the general evolutions of τsim = f (T , P , XAr ,
Φ);  
2
2
2
τcor
• the numerical values of the deduced coefficients: lg = LΦ k · LXj · LPi
τref
θ a, sim , p sim , x sim , and α sim . k=0 j =0 i=0
× (ai,j,k + bi,j,k · IT + ci,j,k · LT).
By considering a wide range of thermodynamic (31)
states and mixture compositions,
These “linear” relations try to conciliate:
• T ∈ [1500 K, 1900 K] ≈ [1225 ◦ C, 1625 ◦ C] ≈
[2240 ◦ F, 2960 ◦ F], centered in Tref = 1700 K ≈ • the prediction precision and the flexibility of
1425 ◦ C ≈ 2600 ◦ F, the detailed mechanisms (knowledge models) for
• P ∈ [10 kPa, 1 MPa] = [100 mbar, 10 bar] ≈ various thermodynamic conditions and mixture
[1.45 psi, 145 psi], centered in Pref = 100 kPa = compositions;
1 bar ≈ 14.5 psi, • the simplicity and the calculation speed of either
• Φ ∈ ([0.4, 1.0] ∪ [1.0, 4.0]), centered in Φref = the semi-empirical correlations or the global re-
1.0, action (both behavior models).
• XAr ∈ [0, 0.7], “centred” in X Ar, ref = 0,
Appendix A shows how:
it thus seems possible to correlate the linearized form
lg(τcor ) = f (T , P , Φ, XAr ) correctly with a mini- (1) to arrive at this polynomial fit through a mathe-
mum set of coefficients. matical development of increasing complexity;
The impact analysis of the influential parameters (2) to accelerate the numerical evaluation of τ cor
suggests to use as reduced variables: (useful mean in the case of an intensive use, as re-
quired in simulation of processes related to com-
T
• IT = 1 − ref (26) bustion behind shocks);
T (3) to efficiently and quickly prepare a kinetic data-
and its correction base;
 
T (4) to simply and rapidly establish the polynomial
LT = lg (27)
Tref coefficients (Moore and Penrose’s analytical res-
to reproduce a modified Arrhenius-type law for olution [35], here explicitly used for four investi-
the temperature (major kinetic factor); gation ranges);
  (5) to evaluate the reproduction performances of
P
• LP = lg (28) τ sim by τ cor :
Pref
• the deviation is lower than 3.5% and often
and its correction LP2 for the pressure; close to 0.5%;
   
XReac 1 − XAr • the calculation is about 106 faster than the
• LX = lg = lg (29)
XReac,ref 1 − XAr,ref step-by-step resolution using S ENKIN, and
performance is comparable with the traditional
and its correction LX2 for the fraction of either semi-empirical correlation (this computational
dilutant X Ar or reactant X Reac ;
  speed-up does not depend on the computer
Φ
• LΦ = lg (30) power, but on the complexity both of the cor-
Φref relation and of the mechanism).
and its correction LΦ 2 for the equivalence ratio.
The slight differences (correlation τcor | reference
τsim ) are satisfactory, for two reasons:
4. Evolution of the ignition delays τ sim simulated
for n-C7 H16 /O2 /Ar (1) The additional relative errors on the modeling,
generated by the correlation, remain negligi-
4.1. General ble compared to the detailed mechanism inac-
curacies: the discrepancies (simulation τsim |
This section and the following one describe the experience τexp are larger than 25%, that, is more
general evolution tendencies of the modified mech- than one order of magnitude higher than the stud-
anism predictions. The study of the ignition delays ied deviations (τcor | τsim ).
396 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408

Fig. 5. Evolution of the correlated ignition delays τ cor , with the equivalence ratio Φ and the temperature T for the mixture
n-C7 H16 /O2 at P ref = 100 kPa: (a) 3D representation of τcor = f (Φ, T ) over the investigated range (log–normal–log scale);
(b) cross sections τcor = fT (Φ) of the cartography, realized at 1500 K, 1600 K, 1700 K, and 1800 K (log–log scale); (c) cross
sections of the cartography, carried out according to the valley: illustration of the evolution with T of the minimum delay τ cor, min
(normal–log scale) and of the associated optimal equivalence ratio Φopt,τ (normal–log scale). Use of Eqs. (A.21) and (A.22),
reproducing the predictions of the modified mechanism (Imbert et al. [1]) with an average deviation about 0.6%.

(2) The absolute errors are too small to deteriorate
the graphics intended to reproduce the evolution
tendencies of τ sim : τ cor constitutes a very good
approximation of τ sim , due to the important vari-
ations of τ sim inside the studied range of condi-
tions.
Taking advantage of these features, the evolution
of the ignition delays τ cor and of the activation ener-
gies θ a, cor will be often represented as tridimensional
isometric plots here. Indeed, illustration of the evolu-
tion tendencies of these parameters enables the dis-
cussion of the validity domain of the mechanism: for
example, Davidson and Hanson [13] used this method
to compare the delays issued from the semi-empirical
correlations with those predicted by the mechanisms
they studied in the case of the combustion of n-
heptane and iso-octane.
4.2. n-C7 H16 /O2 /Ar mixtures diluted and
stoichiometric
For stoichiometric mixtures, either pure or diluted
in argon, the evolution of τ cor with T , P , and X Ar
does not require any particular comments in addition
to those formulated after the two-dimensional analy-
sis. The reason is the important decoupling between
these three kinetic factors: as exposed in Tables 4
and 5, the absolute values of the crossed coefficients
are quite small.
4.3. n-C7 H16 /O2 mixtures pure and with variable
equivalence ratio
The conclusion is not the same for pure mixtures
with variable stoichiometry, as can be shown by the
evolution of τcor = f (Φ, T ) (Fig. 5). In contrast to
the previous case, the thermodynamic parameters (T
or P ) definitely overlap with the equivalence ratio
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
ones, especially for lean mixtures. To quantify this
characteristic, Fig. 5b illustrates cross sections τcor =
fT (Φ) carried out for various constant temperatures.
This graphic shows:
• a variation with Φ of the gap between two sec-
tions established at fixed T , which manifests the
coupling between the parameters;
• a minimum delay τ sim, min and an associated op-
timal equivalence ratio Φopt,τ ≈ 0.3, both pa-
rameters varying with the thermodynamic state
(Fig. 5c).
The optimal kinetic equivalence ratio Φopt,τ in-
creases with T : at higher temperatures, the competi-
tion between RH and O2 to react with ◦ H has less
impact, with regards to the greater production of this
atom. However Φopt,τ remains rather far from the op-
timal thermodynamic one Φopt,DCJ ≈ 2.2 (Imbert et
al. [4]), associated with the maximum of:
• the detonation velocity DCJ ≈ 2400 m s−1 ≈
8640 km h−1 ≈ 5370 mph, corresponding to
Mach 9.4 (whereas for the stoichiometric mixture
DCJ ≈ 2100 m s−1 ≈ 7560 km h−1 ≈ 4700 mph
⇔ Mach 7.2);
• the von Neumann temperature T vN ≈ 1700 K,
which is the average of the extremely heteroge-
neous conditions behind the detonation front;
• the detonation intensity PPvN − 1 ≈ 100.
1 • an experimental investigation to establish a ki-
This discrepancy between kinetic and thermodynamic
constraints qualitatively explains why the highest sen-
sitivity to detonation corresponds to slightly rich mix-
tures (Φ ≈ 1.1, according to Imbert et al. [4]).
Incidentally, the normal scale, reported along the
temperature axis, does not constitute the best choice,
as clearly seen by fixing Φ: τ cor , if plotted versus T
using a logarithmic scale, is submitted to relatively
important inflections. A scale according to T −1 (as
in a standard Arrhenius-type diagram) would be more
suitable for the temperature axis.
5. Evolution of the activation parameters θa,sim
and Ea,sim , simulated for n-C7 H16 /O2 /Ar
5.1. General
This part describes the evolution of the appar-
ent activation factors (temperature θ a, sim and energy
E a, sim ) with:
• the mixture nature (Φ and X Ar );
• the initial pressure P of the shocked medium.
397
θ a, cor and E a, cor were evaluated after the inter-
mediate calculation of three delays τ cor , established
with Eq. (31):
• for the desired operating conditions (P , Φ, and
X Ar );
• at three arbitrary chosen temperatures: 1500,
1700, and 1900 K.
Ea,cor = R · θa,cor represents the slope of the line
ln(τcor ) = f (T −1 ), which best correlates these val-
ues in an Arrhenius-type diagram.
As E a, cor originates from a derivative of τ cor ver-
sus T , particular care has been taken to also check the
continuity of the derivative of τ cor versus Φ. This has
been the case especially, for the connection between
the mixtures (Section 3.5):
• rich: quasi-linear dependence of Lτsim =
fT ,P (LΦ);
• lean: parabolic evolution of Lτsim = fT ,P (LΦ).
The particular features, hereafter exposed, will not
be interpreted: this exercise leaves the framework of
the semi-empirical correlations reformulation and ap-
pears difficult.
As for the analysis of the previous coefficients, a
good interpretation would require:
• a thorough theoretical study of the mechanism;
netic database, statically broad enough to smooth
the evolution trends of the measured delays τ exp ,
and then to calculate trustable local derivatives
E a, exp .
5.2. n-C7 H16 /O2 mixtures pure and stoichiometric
Fig. 6 illustrates the evolution of θa,cor = f (P ),
for the reference mixture. For a given composition,
θ a, cor grows with P and seems to tend toward a max-
imum θa,cor,max ≈ 19.6 × 103 K (E a, cor, max ≈ 163
kJ mol−1 ≈ 39.0 kcal mol−1 ), which is approached in
the vicinity of P opt ≈ 1 MPa = 10 bar ≈ 145 psi.
5.3. n-C7 H16 /O2 /A mixtures diluted and
stoichiometric
Fig. 7 illustrates the evolution of θa,cor =
f (P , XAr ) of the stoichiometric mixture n-C7 H16 /
O2 /Ar. θ a, cor seems:
• to tend toward the maximum θa,cor,max ≈ 19.6 ×
103 K located close to P opt = 1 MPa, for a given
composition (here fixed X Ar );
• to differently evolve with X Ar according to P :
398 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
Fig. 6. Evolution of the correlated activation temperature
θ a, cor with the pressure P (log–normal scale) for the mix-
ture n-C7 H16 /O2 , Φref = 1. Use of Eq. (A.19), reproducing
the predictions of the modified mechanism (Imbert et al. [1])
with an average deviation about 0.3%.
Fig. 7. Evolution of the correlated activation temperature
θ a, cor with the inert fraction X Ar and the pressure P
(normal–log–normal scale) for the mixture n-C7 H16 /O2 /Ar,
Φref = 1. Use of Eq. (A.20), reproducing the predictions of
the modified mechanism (Imbert et al. [1]) with an average
deviation about 0.3%.
– θ a, cor decreases with X Ar for low pressures
(P ≈ 10 kPa);
– θ a, cor seems not very sensitive to dilution for
high pressures (P ≈ 103 kPa).
5.4. n-C7 H16 /O2 mixtures pure and with variable
equivalence ratio
Fig. 8 illustrates the evolution of θa,cor = f (P , Φ)
of the mixture n-C7 H16 /O2 . In Fig. 8a, θ a, cor seems:
Fig. 8. Evolution of the correlated activation temperature
θ a, cor with the equivalence ratio Φ and the pressure P for
the mixture n-C7 H16 /O2 : (a) 3D representation of θa,cor =
f (Φ, P ) over the investigated range (log–log–normal scale);
(b) cross sections θa, cor = fP (Φ) of the cartography real-
ized at 1.0 MPa, 316 kPa, 100 kPa, 31.6 kPa, and 10.0 kPa
(log–normal scale). Use of Eqs. (A.21) and (A.22), repro-
ducing the predictions of the modified mechanism (Imbert
et al. [1]) with an average deviation about 0.6%.
• to increase with P and then to decrease for a
given composition (here fixed Φ): for rich mix-
tures (Φ  1.25), the observed maximum is at-
tained for P  103 kPa;
• to reach its maximum at Φ ≈ 1, by varying Φ
and fixing P ∈ [36 kPa, 900 kPa] = [360 mbar,
9.0 bar] ≈ [5.2 psi, 130 psi] (Fig. 8b): it appears
as a crest line (well approximated in Fig. 6, re-
lated to the stoichiometric mixture).
This inclination change (discontinuity of the second
derivative of τ cor , first established from T to form
θ a, cor , then from Φ) would remain undetectable with-
out the use of a systematic calculation technique, as
outlined here. This particularity cannot be entirely at-
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408 399

tributed to Eqs. (A.21) and (A.22), since these corre- In Appendix A, the mathematical way to build and
lations reproduce the simulated delays τ sim with an optimize this new formalism, as well as characterize
average deviation close to 1.5%. This characteristic its performances, was explained.
seems to result from an artifact of the detailed mech-
anism, not interpreted here for the previously men- (1) The correlation of τ sim by τ cor , thanks to a gen-
tioned reasons. eralized development in Taylor series [36], was
proved to be meaningful using simultaneously
the four factors T , P , X Ar , and Φ:
6. Conclusion and perspectives: Potentialities of  
2
2
2
the advanced correlations τ
lg = LΦ k · LXj · LPi
τref
k=0 j =0 i=0
The main motivation concerning this article was
the rapid, easy, and precise evaluation of the ignition × (ai,j,k + bi,j,k · IT + ci,j,k · LT)
delays, from global parameters describing the ther- (Eq. (31)).
modynamic state, and the composition of the reactive
(2) A kinetic database, composed of 5N delays for
mixture. The method, a particular adaptation of the re-
N ∈ [1, 4] parameters and quickly prepared was
promodeling philosophy, was developed considering
proved to be large enough if efficiently designed
the particular case of high-temperature combustion
using strategic conditions.
(occurring behind shock waves or detonation fronts)
(3) The coefficients τref , . . . , ci,j,k (here expressed
of n-heptane, supposed to be a good model fuel for
for N = 4), solutions of a quasi-linear over-
PDE.
sized equation system, can be rapidly and ex-
These specificities explain why the work presented
actly determined, applying the Moore and Pen-
here was inspired by the traditional semi-empirical
rose pseudo-inverse [35], a no-iterative analytical
correlations, which have recognized abilities to repro-
process.
duce ignition delays.
(4) A way to speed up the evaluation of the poly-
In Section 2, the fits τ cor were interpreted:
nomials simply by organizing the calculation to
reduce its complexity was explained.
(1) by reformulating them, starting from the param-
(5) The orders of magnitude of the durations re-
eters T , P , Φ, and X Ar ;
quired to evaluate the traditional correlation, the
(2) by explaining the four dependence types between
new formalism, and to use S ENKIN with the de-
the delays τ and these kinetic factors, using well-
tailed mechanism, were quantified and then com-
established theoretical models: Arrhenius [14],
pared.
Lindemann et al. [23], etc.;
(6) The typical deviations between the simulated de-
(3) by physically analyzing the coefficients θ a, cor ,
lays τ sim and their fits τ cor were evaluated.
α cor , p, and x deduced from these relations.
Last, using Eq. (31), some general features of the
Then in Section 3, the transposition of this classi-
mechanism were exhibited in Sections 4 and 5:
cal formalism to a detailed mechanism was discussed.
The analysis of the impact of T , P , X Ar , and Φ on the
(1) The delay τcor = f (T , P , Φ, XAr ) evolves in a
delays τ sim , simulated by the version of the Curran et
complex way with Φ, due to the strong coupling
al. model [6,7], slightly modified by Imbert et al. [1],
of this parameter with the thermodynamic state
allowed us:
(T or P ).
(2) The activation temperature θa,cor = f (P , Φ,
(1) to exhibit similar evolutions for the mechanism
XAr ) exhibits an unexpected maximum around
and the semi-empirical correlations: only the de-
stoichiometry, marked by an inclination change.
pendence {τsim | Φ} differs, especially for fairly
This observation remains difficult to experimen-
lean mixtures;
tally confirm, other than indirectly by deriving
(2) to find good agreement between the coefficients
the order of magnitude of the measured delays
θ a , α, p, and x, deduced both from the semi-
Ln(τexp ) versus T −1 .
empirical correlations and from the mechanism;
(3) to define five reduced variables (cf. Section 2.6),
The performances of these new correlations were
intended to be kinetically significant:
checked with ignition delays τsim = f (T , P , Φ, XAr ),
• IT = 1− TTref , LT = lg( TT ), and LP = lg( PP ) simulated by a mechanism and not empirically deter-
ref ref
for the thermodynamic state; mined, due to the lack of measurements to establish
1−XAr
• LX = lg( 1−X ) and LΦ = lg( ΦΦ ) for the an experimental kinetic database, broad and diversi-
Ar,ref ref
mixture nature. fied enough.
400 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
The polynomial interpolations τ cor seem satisfac-
tory, since they reproduce the delays τ sim with a good
precision in comparison with the reliability to predict
τ sim using the original detailed mechanism: in the
most unfavorable case, the 3.5% deviation of {corre-
lation τ cor | reference τ sim } appears lower, by almost
one order of magnitude, than the uncertainties ris-
ing from simulations (discrepancies {modeling τ sim
| experiment τ exp } estimated at more than 25%, ac-
cording to Imbert et al. [1]).
In addition, this method is really flexible to use,
considering:
• the number of kinetic factors N ∈ [1, 4] (here se-
lected among T , P , Φ, and X Ar ), likely to be
simultaneously investigated;
• the broad range of investigated conditions (no ex-
haustive values, here chosen for a later kinetic
analysis of n-heptane detonation), resulting from
the combination of the domains:
– T ∈ [1500 K, 1900 K];
– P ∈ [10 kPa, 1 MPa];
– XAr ∈ [0, 0.7];
– Φ ∈ [0.25, 4.0].
Moreover, the computational speed up is:
• important: computation about 3 × 106 faster than
the step-by-step resolution of the numerous dif-
ferential equations, using S ENKIN;
• comparable with the traditional semi-empirical
correlation one: calculation time only 13 times
longer.
This noticeable gain does not really depend on the
computer power, but on the complexity of both the
correlation and the mechanism. The performances
have been evaluated here for a polynomial with two
parameters (i.e., 32 = 9 coefficients), reproducing a
detailed model composed of 565 species and 2538 re-
actions.
Last, from a technical point of view, this construc-
tion method respects two other quality modeling stan-
dards:
• retaining the physical meaning: fidelity to the
empirical Arrhenius rate law [14] and to its adap-
tation by Lifshitz et al. [16], for example;
• limiting the number of adjustment parameters
(3N  81 coefficients, here for N ∈ [1, 4]),
and offering the possibility to interpret these
terms.
Because of its interpolation quality in a wide range
of conditions, this new type of correlation can first be
used during the development phase, or the validation
stage of a mechanism:
(1) to highlight and to compare the general evolution
tendencies of the delays:
• τ exp , empirically measured (prerogative tra-
ditionally dedicated to the semi-empirical
Arrhenius-type correlations);
• τ sim , simulated by a kinetic model (as here,
with n-heptane oxidation);
(2) to notice, with an already built mechanism, cer-
tain troubles difficult to be detected without a tool
dedicated to the systematic estimation of τ sim :
crest-line of θa,cor = f (Φ, P ), for example;
(3) to facilitate the targeting of operating conditions
in an experimental device (shock tube or rapid
compression machine) by predicting strategic
ones to validate a model thanks to τ exp .
In the case of the modeling of the high-temperature
combustion, the suggested method can also constitute
an alternative to the classical mechanism reduction,
since it conciliates:
(1) the powerful data processing of both empirical
correlations and global reaction models, tech-
niques largely employed today in computational
simulations, due to the intensive calculations of
reaction rate progress, related to mesh grids with
a significant number of nodes;
(2) the precision and flexibility of the detailed mech-
anisms, provided that the “freezing” of the influ-
ence of the neighborhood on the chemistry dur-
ing the autoignition does not constitute a severe
oversimplification;
(3) the ease and rapidity of use, which make it quasi-
directly available to researchers from all special-
ities, with little effort and without the need of
specific tools.
In particular, this new polynomial expression can
be perfectly integrated in the modeling of the com-
bustion behind a shock front, since it can be em-
ployed:
(1) directly with the traditional ZND model for a
global “0D” interpretation of the kinetic proper-
ties of a CJ-type self-sustained detonation;
(2) as calculation intermediaries to evaluate the re-
action rate progress, in multidimensional com-
plex processes (detonation diffraction, transition
from deflagration to detonation, . . . ): the de-
lays remain so short (few microseconds) that
mass and energy transfers (otherwise than in-
duced by shock wave complexes) can be ne-
glected.
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
These remarks emphasize the limitations of this
process, which remain comparable with those of the
semi-empirical correlations and of the behavior mod-
els, generally speaking:
(1) Lack of modularity: as with “purely mathemati-
cal” models, this black box only reproduces one
fixed image of the original kinetic model, which
must have been previously validated. However,
the wasted time resulting from a mechanism re-
vision remains modest taking into consideration
the profit likely to rise from its later intensive use
in CFD;
(2) Loss of precision while extrapolating far from
the domain related to the database establish-
ment;
(3) “Freezing” of chemistry: the mass transfer seems
to prohibit the use of this means to simulate tra-
ditional engines or turbines. Since temperatures
attained in deflagrations are lower, the involved
reaction times, of about several milliseconds, al-
low the displacements and the mixing of active
species over distances not negligible compared
to typical sizes of the enclosure, and so of the
mesh grid.
More elaborate models (based on this polynomial
formalism) could reproduce the kinetic impact of a
thermodynamic change due to external reasons during
the induction process. So the rapid variation of tem-
perature and pressure generated by the shock waves
propagation could be taken into account.
A notable improvement to definitely break the
“freezing” of the autoignition chemistry would thus
consist of taking into account the influence of the
neighborhood, concerning concentrations of active
species.
This limitation currently restricts the use of this
correlation to hot combustions, very fast compared
to the mass transfers (so with a Damköhler number
Da
1), like those related to PDE. By aiming at this
objective, it may be possible in the future to take into
account the external modifications of key reactional
concentrations (related to the pool of atoms and rad-
icals active during the propagation stage). The ideal
would then be to manage to build independent re-
duced variables, able to be easily incorporated into
polynomial expressions similar to the one presented
here.
Acknowledgments
The authors thank Dr. Henry Curran, from NUI
Galway, for supplying his detailed kinetic model.
401
Appendix A. Development of the polynomial
correlations and calculation of the related
performances and uncertainties
A.1. General method to extend the Arrhenius-type
formalism
A.1.1. Correlation with fixed coefficients
The correlation with fixed coefficients constitutes
the simplest Arrhenius-type expression to be built,
starting from the parameters IT, LT, LP, LX, and LΦ:
 
τcor
Lτ = lg
τref,0
= −θ · IT + t · LT + p · LP + p · LP2
+ x · LX + x  · LX2 + φ · LΦ + φ  · LΦ 2 .
(A.1)
As the time constant is expressed inside lg(τref,0 ), the
logarithm of the dimensionless duration Lτ quite nat-
urally provides the reaction delay, according to:
τ = τref,0 · 10Lτ ⇔ (A.2a)
 
τcor
Lτ = lg = f (T , P , Φ, XAr ). (A.2b)
τref,0
Expression (A.1) constitutes only a slight adaptation
of the linearized version of the semi-empirical cor-
relation (Eq. (12)). The addition of second-order cor-
rective terms and the reformulation of the dependence
{τcor | Φ} obviously improve the capacities to repro-
duce the reference delays τ sim . However, the posi-
tive impact only remains localized in the vicinity of
the development center (here related to the conditions
chosen as references).
A.1.2. Local development around the center of the
domain
Correlation (A.1) suffers from the non-adaptability
of its coefficients. In fact, to preserve a good repro-
duction quality, it would be necessary:
• either to strongly restrict the applicability range,
as do the majority of the users of semi-empirical
correlations;
• or to vary the coefficients, versus parameters they
do not directly correlate with; for example, even
if the simulations show a slow dependence, the
pressure coefficient p should slightly evolve with
T , X Ar , and Φ.
By aiming at this last point, it is possible to develop
Eq. (A.1), according to the four considered factors
(T , P , X Ar , and Φ). The use of the Taylor series
[36], limited to the vicinity of the reference condition
402 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408

τref = f (XAr,ref , Φref , Pref , Tref ), provides: • limiting the calls of time-consuming functions:
  namely inverses, logarithms, and powers related
τcor to real exponents;
Lτ = lg
τref • using an appropriate factorization, i.e., replacing
= [1 + a0 · LΦ + a0 · LΦ 2 ] the sum of terms containing powers bounded to
entire exponents, by a series of simple additions
× [1 + b0 · LX + b0 · LX2 ] and multiplications.
× [1 + p0 · LP + p0 · LP2 ]
Consequently, the first step consists of determining
× [1 + t0 · LT − θ0 · IT] − 1. (A.3) the reduced variables, which evaluations are impossi-
ble to avoid (among IT, LT, LP, LX, and LΦ), once for
A.1.3. Generalization of the development to the each condition. In principle, it is then enough to es-
whole domain tablish the correlation, while taking as a starting point
The development of the Taylor series, written ac- the following example. By supposing that a second-
cording to the factorized form (Eq. (A.3)) exhibits order polynomial correctly reproduces each evolution
terms additional to those shown by relation (A.1): the {τ sim | kinetic factor}, it is a matter of evaluating
new crossed coefficients take into account a coupling the following line vectors V 1,n . With their N com-
between each parameter. The overlap of the param- ponents, they can exhibit the simultaneous influence
eters {RT or LT}, LP, LX, and LΦ complicates the of:
polynomial, but partially meets the formulated need
for flexibility. It is possible to improve the adaptabil- • T:
ity by suppressing the constraints implicitly imposed
by factorization with: VT1,3 = ( 1 IT LT ) ; (A.4a)
  • T and P :
τcor
Lτ = lg  
τref,0 VTP1,9 = VTP(0) V (1)
TP1,3
V
TP1,3
(2) , (A.4b)
1,3

2
2
2
with:
= LΦ k · LXj · LPi
k=0 j =0 i=0 V = VTP1,3 , (A.4c)
(0)
TP1,3
× (ai,j,k + bi,j,k · IT + ci,j,k · LT)
V (1) = LP · V (0) , (A.4d)
TP1,3 TP1,3
(Eq. (31)).
V (2) = LP · V (1) ; (A.4e)
Here the implicit time constant τ ref, 0 (deduced from TP1,3 TP1,3
the coefficients resolution) borders τ ref , the delay di- • T , P , and X Ar :
rectly predicted for the reference condition. The re-  
production of τ sim remains good not only in the vicin- VTPX = V
1,27 TPX1,9
(0) V
TPX1,9
(1) V
TPX1,9
(2) ,
ity of the development center (as for any Taylor se- (A.4f)
ries), but also in the whole range, due to the explicit
with:
generalization of the coupling between parameters.
If the number of coefficients 3N (for N parame- V (0) = VTP1,9 , (A.4g)
ters) appears too important, for an easy and fast han- TPX1,9
dling, it seems necessary to subdivide the correlation V (1) = LX · V (0) , (A.4h)
TPX1,9 TPX1,9
validity range. This simplification enables the preser-
vation of good agreement with the detailed mecha- V (2) = LX · V (1) ; (A.4i)
TPX1,9 TPX1,9
nism, while limiting the inflation of adjustment pa-
• T , P , X Ar , and Φ:
rameters.
VTPXΦ1,81
A.2. Optimization of the polynomial evaluation  
= VTPXΦ (0) V
TPXΦ1,27
(1) V
TPXΦ1,27
(2) ,
1,27
A.2.1. Theoretical principle (A.4j)
The evaluation of the correlated delay τ cor can be with:
accelerated on computer by decreasing the number of
complex operations necessary to its calculation. This V (0) = VTPX1,27 , (A.4k)
TPXΦ1,27
traditional algorithm in data processing here consists
of: V (1) = LΦ · V (0) , (A.4l)
TPXΦ1,27 TPΦ1,27
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408 403

V (2) = LΦ · V (1) . (A.4m) • [Ar]0.09 not taken into account;

TPXΦ1,27 TPXΦ1,27
• [C7 H16 ] and [O2 ] previously established starting
These stages finally enable the building of V TPXΦ 1,81 , from X C7 H16 , X O2 , T , and P , with Eq. (3).
representative of the mixture conditions:
So the calculation time related to the new formalism
VTPXΦ1,81 = (1 IT LT LP LP · IT appears:

LP · LT LP2 LP2 · IT ... • only 13 times longer than the one bounded to the
LΦ 2 · LX2 · LP2 · LT). (A.5) classical correlation;
• about 3×106 times shorter than the one linked to
The scalar product of this line vector with the col- the simulation using C HEMKIN.
umn vector C 81,1 (composed of the polynomial coef-
ficients) provides Lτ , the logarithm of the correlated Obviously, this important improvement depends on
delay τ cor , scaled by τ ref, 0 : the complexity of:
 
τcor
Lτ = lg = VTPXΦ1,81 · C81,1 . (A.6) • the polynomial, which decreases with the number
τref,0 of coefficients (3N rising itself with the number
N ∈ [1, 4] of kinetic factors);
A.2.2. Performance analysis
• the original mechanism, which increases with the
To quantify the evaluation duration of the corre-
number of species and reactions.
lated delay τ cor , these vectorial operations have been
carried out:
A.3. Analytical resolution of the polynomial
coefficients
• with a Pentium III running at 500 MHz;
• on M ATLAB 6.1 (interpreted language, especially
dedicated to matrix algebra); A.3.1. Theoretical principle
• by considering a correlation with 9 coefficients This passage shows how to optimize the 3N coef-
(restricted to 2 parameters: T and P ); ficients (noted from a 0,0,0 to c2,2,2 ), that is, to min-
• while taking as previously established parame- imize the difference between the delays τ sim (sim-
ters: ulated by the mechanism and used as references)
– T = 1800 K ≈ 1525 ◦ C ≈ 2780 ◦ F; and τ cor (evaluated with this new correlation), for
– P = 200 kPa = 2.0 bar ≈ 29 psi; the whole conditions described by an existing kinetic
– the polynomial coefficients, and among them: database.
a0,0,0 = lg(τref,0 ). Using the formalism of Eq. (31), this condition
corresponds to solving the following oversized equa-
Under these conditions, 107 loop repetitions have en- tion system (i.e., with more constraints than unknown
abled the estimation of the total duration at 308 µs, as factors):
well as the percentages of the computing times dedi-
⎧ 2 2 j
cated to each stage: ⎪ 2 k i
⎪
⎪ k=0 j =0 i=0 LΦ1 · LX1 · LP1
⎪
⎪
⎪
⎪ × (ai,j,k + bi,j,k · RT1 + ci,j,k · LT1 )
• evaluation of the variables IT, LT, and LP (Eqs. ⎪
⎪
⎪
⎪ ≈ lg(τsim,1 ),
(26)–(28)): 174 µs ⇔ 56.6%; ⎪
⎪
⎪
⎪ 2 2 2
• determination of the line vector V TP1,9 , by com- ⎪
⎪ k=0 j =0 i=0 LΦ2k · LX2 · LPi2
j
⎪
⎪
bination (Eqs. (A.4a)–(A.4e)): 98 µs ⇔ 32.0%; ⎪
⎨
• calculation of the scalar product (Eq. (A.6)): × (ai,j,k + bi,j,k · RT2 + ci,j,k · LT2 )
26 µs ⇔ 8.4%; ⎪ ≈ lg(τsim,2 ),
⎪
⎪
⎪
⎪
⎪ ..
• passage to the exponent according to τcor = 10Lτ ⎪
⎪ .
⎪
⎪
(Eq. (A.2)): 9.0 µs ⇔ 3.0%. ⎪
⎪  2 2
⎪
⎪ 2 k j i
⎪
⎪ k=0 j =0 i=0 LΦM · LXM · LPM
⎪
⎪
The estimation of τ sim using S ENKIN, by an iterative ⎪
⎪ × (ai,j,k + bi,j,k · RTM + ci,j,k · LTM )
⎩
resolution of the whole differential equations associ- ≈ lg(τsim,M ). (A.7)
ated to the detailed mechanism (2538 reactions and
565 species), was approximately 15 min. By adopting as a criterion the least-squares tech-
The time needed to evaluate Imbert et al. semi- niques, and weighting each of the M terms by Wl ,
empirical correlation (Table 2) was 24 µs, under sim- the objective function to be optimized can be written
ilar calculation conditions: as
404 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408

f (a0,0,0 , . . . , c2,2,2 ) Matrix

Weighted mixture description: thermodynamic state
 2 2 2

M j
and composition
= LΦlk · LXl · LPil ⎛√ ⎞
W1 · V (1)
l=1 k=0 j =0 i=0 TPXΦ1,81
⎜ √ ⎟
⎜ W2 · V (2) ⎟
⎜ TPXΦ1,81 ⎟
× (ai,j,k + bi,j,k · RTl + ci,j,k · LTl ) MM,81 = ⎜ ⎟. (A.11)
⎜ .. ⎟
⎜ . ⎟
2 ⎝√ ⎠
WM · V (M)
− lg(τsim,l ) · Wl . (A.8) TPXΦ1,81
Column vector
Delays τ sim simulated by the model and weighted
Several numerical optimization methods would
⎛ √ ⎞
√W1 · lg(τsim,1 )
enable the solving of system (A.8):
⎜ W2 · lg(τsim,2 ) ⎟
⎜ ⎟
• analytical ways, generally based on the gradients: TM,81 = ⎜ .. ⎟. (A.12)
⎝ . ⎠
improvement of Newton and Raphson’s original √
principle [37,38]; WM · lg(τsim,M )
• heuristic processes (also known as stochastic or Column vector
geometrical): exploration of the space by suc- Polynomial coefficients to be solved (notation
cessive tests and temporary assumptions to re- Eq. (31))
search the most favorable directions: the Nelder ⎛ ⎞
a0,0,0
and Mead simplex [39], for example; ⎜ b0,0,0 ⎟
• metaheuristic means, improvements of the previ- ⎜ ⎟
⎜ ⎟
ous methods, employed to solve the difficult arti- C81,1 = ⎜ c0,0,0 ⎟ . (A.13)
⎜ . ⎟
ficial intelligence problems: the Schwefel evolu- ⎝ .. ⎠
tion strategy [40], for example. c2,2,2
This linear optimization problem can be directly
The choice of an optimization process is not without solved using the analytical method developed by
consequence, since it can: Moore in 1920 and published by Penrose [35].
This matrix algorithm, based on the evaluation of
• converge only at the end of an important series of
iterations, and so notably lengthen the calculation • Moore’s pseudo-inverse matrix:
time;
• block on a simple local optimum, and thus not †† M t −1 · t M
81,N = ( MN,81 · MN,81 ) N,81 ;
provide the expected global minimum;
(A.14)
• sometimes require a delicate adjustment of the
initial conditions, to avoid the previous nui- • the vector solution:
sances.
C81,1 = †† M81,N · TN,1 ; (A.15)
In this case, as equation system (A.7) is intentionally
gives in less than one second the exact solution when
quasi-linear, the research of least-squares becomes it is programmed with M ATLAB (the Moore pseudo-
very simple. It is enough: inverse can be evaluated by the function pinv).
Note: As Tables 4–7 show, the polynomial con-
• to minimize stant (first component of the column vector C81,1 ) is
not written as it was originally, but retranscribed in
f (a0,0,0 , . . . , c2,2,2 ) the more explicit form of a pseudo-reference delay

= MN,81 · C81,1 − TN,1 2 ; (A.9) τref,n = 10a0,0,0 . (A.16)

τref,n appears very close to the delay τ ref simulated
• that is, to obtain
using C HEMKIN, for the reference conditions.

MN,81 · C81,1 ≈ TN,1 , (A.10) A.3.2. Choice of the kinetic database

Detailed mechanism characteristics were recorded
with the following elements: in the form of a base of M data, including:
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
• the thermodynamic state of the reactive medium
(RT, LT, and LP established from T , P ) to evalu-
ate MM,81 (matrix (A.11));
• the nature of the initial mixture (LX and LΦ eval-
uated from X Ar and Φ) to determine MM,81 ;
• the simulated times (Lτ established from τ sim )
resulting from the choice of these conditions
and employed to calculate TM,81 (column vec-
tor (A.12)).
To shorten the resolution stage of the polynomial
coefficients, it appears possible to restrict the database
size to M = 5N key values (for N parameters). These
selected conditions should correspond to grid nodes:
• regularly spaced, within sight of the typical ki-
netic evolution scales, for each parameter (see
the definition of the reduced variables IT, LP, LX,
and LΦ) (Eqs. (26)–(30));
• astutely placed to minimize the distance between
two consecutive nodes by taking into considera-
tion a suitable norm for the studied space, which
dimension is N .
Then, the weights Wl of each condition depend on:
• the prediction reliability, which is here nearly the
same for all the delays τ sim , due to:
– the good coverage between the mechanism va-
lidity range and the domain conditions used;
– the retention of the tolerance to evaluate τ sim
(defined by the time interval DELT for solu-
tion printouts, in the C HEMKIN input file);
– the automatic procedure to determine τ sim ,
starting from the time profile of [◦ OH];
• the strategic position of the chosen condition,
within the mesh grid: the weighting (left to the
arbitrary choice of the user) is worth here:
– 3, for the extreme or central positions, accord-
ing to the considered kinetic scale;
– 2, for intermediate, and regularly spaced, po-
sitions;
– 1, for randomly generated conditions.
Once these precautions are taken, the resolution
time of the polynomial corresponds to the duration
needed to prepare the database. Thus to analyse n-
C7 H16 /O2 /Ar mixtures, 53 × 15 = 1875 min (31.5 h,
or 1.3 days) is needed, using a Pentium III, 500 MHz).
These calculations enable the reproduction of the sim-
ulated delays τ sim , with an average deviation of 0.3%,
over the broad domain simultaneously covering:
• T ∈ [1500 K, 1900 K];
• P ∈ [10 kPa, 1 MPa];
• XAr ∈ [0, 0.7];
405
• Φ = 1.0.
A.4. Evaluation of the deviation
{correlation τcor | simulation τsim }
Here, the average dispersion {correlation τcor |
reference τ sim } will not be expressed using the Pear-
son correlation coefficient χ 2 [41]. Indeed, as the
analysis relates to a comparison between orders of
magnitude in time, for a fast interpretation, it seems
more explicit to use a definition inspired by the stan-
dard geometrical deviation:

 N   τcor (i) 2 
i=1 ln τsim (i)
Gτcor = exp
N
 1. (A.17)
The reproduction quality by the polynomial correla-
tions remains good: Gτcor  1.05 is verified for the
four explicit correlations, when Gτcor = 1 corre-
sponds to the equality between τ cor and τ sim . Con-
sequently, the discrepancy can be expressed by a rel-
ative deviation, more natural:
τcor = 100(Gτcor − 1)  5%. (A.18)
A.5. Characteristics of the polynomial correlations
in the case of n-heptane autoignition
A.5.1. General
This part clarifies the general correlation (Eq. (31))
in the particular cases of four investigation ranges de-
fined to analyse the kinetic properties related to the
detonation of n-heptane/oxygen mixtures:
• not diluted and stoichiometric: XAr = 0 and
Φ = 1;
• not diluted and rich: XAr = 0 and Φ ∈ [1.0, 2.5];
• not diluted and lean: XAr = 0 and Φ ∈ [0.25,
1.0];
• diluted in argon and stoichiometric: X Ar ∈
[0, 0.7] and Φ = 1.
This division of the investigation range has enabled
the limitation of the total number of coefficients, with-
out deteriorating the reproduction quality, on the large
domain related to the thermodynamic state:
• T ∈ [1500 K, 1900 K];
• P ∈ [10 kPa, 1 MPa].
A.5.2. n-C7 H16 /O2 mixtures pure and
stoichiometric
Table 4 lists the coefficients of the polynomial
406 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408
 
τcor + LP · (u2 + v2 · IT + w2 · LT)
lg = (a1 · IT + b1 · LT)
τref,1 
+ LP2 · (x2 + y2 · IT + z2 · LT) .
+ LP · (c1 + d1 · IT + e1 · LT)
(A.20)
+ LP2 · (f1 + g1 · IT + h1 · LT).
Correlation (A.20) provides the delays τ cor associ-
(A.19) ated with the mixture (n-C7 H16 /O2 /Ar, Φ = 1.0, X Ar
Correlation (A.19) provides the delays τ cor associ- ∈ [X Ar, ref = 0, 0.7]). The relative deviation {τcor |
ated with the mixture (n-C7 H16 /O2 , Φ = 1.0). The τsim } is lower than 1.5% (0.3% on average) for:
average deviation {τcor | τsim } compared to the model
predictions is lower than 1.5% (0.3% on average) for: • 73 time values τ sim a priori used to establish the
database;
• 15 time values τ sim a posteriori evaluated for
• 29 time values τ sim a priori used to establish the
random conditions.
database;
• 10 time values τ sim a posteriori evaluated for
The coefficients analysis shows that:
random conditions.
(1) the terms τ ref, 2 , a2 − h2 remain almost the same
Due to the slow and regular evolution of the delays as their counterparts (τ ref, 1 , a1 − h1 ) related to
τ sim with T and P , it appears reasonable to assume the reference composition, a consequence of the
that the relative deviation between the simulations lost influence of the terms i2 − z2 (related to the
τ sim and their correlations τ cor remains lower than powers in LX) when the mixture is no longer di-
1.5% for the whole range of conditions. luted with argon (XAr = 0 and LX = 0);
The coefficients analysis shows that: (2) the higher order terms j2 − q2 and s2 − z2 (re-
lated to LX and LX2 ) often remain smaller than
(1) τ ref,1 remains very close to τref = 5.95 µs de- their counterparts a2 − h2 of the reference mix-
lay predicted by the mechanism for the refer- ture, a result of the lost influence of the corrective
ence condition (Tref = 1700 K, Pref = 100 kPa, terms, related to the high-order powers of LX.
Φref = 0 and XAr,ref = 0);
(2) the high absolute value of the coefficients a1 − b1 These properties are typical of the developments in a
(related to LT) compared to c1 − h1 (bounded Taylor series, limited around a central point, to which
to LP) confirms the greater influence of the rela- the function converges. In this case, these character-
tive fluctuations of T (than those of pressure P ) istics are remarkable due to the selected formalism:
around the central position; thus, the importance of optimizing the form of the
dimensionless kinetic variables, in order to obtain a
(3) the coefficients d1 − h1 , associated with the high-
rapid convergence.
order terms (products of IT, LT and LP), remain
lower than a1 − b1 , as a consequence of the
A.5.4. n-C7 H16 /O2 mixtures pure and with variable
weak influence on Lτ of the corrective terms
equivalence ratio
intended to reproduce the correlation curvatures
Tables 6 and 7 list the coefficients of the polyno-
(Sections 3.1 and 3.2).
mials
 
τcor
A.5.3. n-C7 H16 /O2 /Ar mixtures diluted and lg = (a3 · IT + b3 · LT)
τref,3
stoichiometric
+ LP · (c3 + d3 · IT + e3 · LT)
Table 5 lists the coefficients of the polynomial
+ LP2 · (f3 + g3 · IT + h3 · LT)
  
τcor
lg = (a2 · IT + b2 · LT) + LΦ · (i3 + j3 · IT + k3 · LT)
τref,2
+ LP · (l3 + m3 · IT + n3 · LT)
+ LP · (c2 + d2 · IT + e2 · LT) 
+ LP2 · (o3 + p3 · IT + q3 · LT) ,
+ LP2 · (f2 + g2 · IT + h2 · LT)
 (A.21)
+ LX · (i2 + j2 · IT + k2 · LT)  
τcor
+ LP · (l2 + m2 · IT + n2 · LT) lg = (a4 · IT + b4 · LT)
τref,4

+ LP2 · (o2 + p2 · IT + q2 · LT) + LP · (c4 + d4 · IT + e4 · LT)

+ LX2 · (r2 + s2 · IT + t2 · LT) + LP2 · (f4 + g4 · IT + h4 · LT)
 B. Imbert et al. / Combustion and Flame 155 (2008) 380–408

+ LΦ · (i4 + j4 · IT + k4 · LT)
+ LP · (l4 + m4 · IT + n4 · LT)
 [1] B. Imbert, L. Catoire, N. Chaumeix, C.E. Paillard, J.
+ LP2 · (o4 + p4 · IT + q4 · LT)

+ LΦ 2 · (r4 + s4 · IT + t4 · LT)
+ LP · (u4 + v4 · IT + w4 · LT)
 [3] B. Imbert, L. Catoire, N. Chaumeix, G. Dupré, C.E.
+ LP2 · (x4 + y4 · IT + z4 · LT) .
(A.22)
Correlations (A.21) and (A.22) provide the delays
τ cor associated with n-C7 H16 /O2 mixtures, respec-
tively rich (Φ ∈ [(Φref = 1.0), 2.5]) and lean (Φ ∈
[0.25, (Φref = 1.0)]). The relative deviation {τcor |
τsim } remains lower than:
(1) 1.5% (0.3% on average) for the first-order poly-
nomial in LΦ, considering:
• 48 time values τ sim a priori used to establish
the database;
• 12 time values τ sim a posteriori evaluated for
random conditions;
(2) 3.5% (0.6% on average) for the second-order
polynomial in LΦ, considering:
• 59 time values τ sim a priori used to establish
the database;
• 18 time values τ sim a posteriori evaluated for
random conditions.
The coefficient analysis shows that:
(1) the difference {correlation τcor | reference τsim }
appears larger than in the previous cases, due to:
• the complex evolution of τsim = f (Φ), not
easily reproducible with low-order polynomi-
als;
• the additional need to check the quasi-tangency
of the correlations related to rich and quite lean
mixtures (use of the stoichiometric composi-
tion as the connection zone);
(2) the coefficients τ ref, 3 , a3 −h3 and τ ref, 4 , a4 −h4
remain comparable to their counterparts τ ref, 1 ,
a1 − h1 defined for the reference mixture, a con-
sequence (as in the diluted case) of the lost influ-
ence of the corrective terms i3 − q3 and i4 − z4
(related to the powers of LΦ) for mixtures ap-
proaching stoichiometry (Φ = 1 and LΦ = 0);
(3) the impact of Φ is more marked on τ , than the
X Ar one:
• the absolute values of the high-order coeffi-
cients i3 − q3 and i4 − z4 remain more impor-
tant than their counterparts related to the argon
addition i2 − z2 ;
• the basic terms a3 −h3 and a4 −h4 differ more
from the reference mixture ones a1 − h1 than
from the diluted compositions ones a2 − h2 .
407
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