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Culture Documents
Gautam Kalghatgi
Gautam Kalghatgi
www.elsevier.com/locate/combustflame
Received 30 June 2004; received in revised form 29 October 2004; accepted 24 November 2004
Available online 23 December 2004
Abstract
Auto-ignition of fuel mixtures was investigated both theoretically and experimentally to gain further understanding of the fuel chemistry. A homogeneous charge compression ignition (HCCI) engine was run under different
operating conditions with fuels of different RON and MON and different chemistries. Fuels considered were
primary reference fuels and toluene/n-heptane blends. The experiments were modeled with a single-zone adiabatic model together with detailed chemical kinetic models. In the model validation, co-oxidation reactions
between the individual fuel components were found to be important in order to predict HCCI experiments, shocktube ignition delay time data, and ignition delay times in rapid compression machines. The kinetic models with
added co-oxidation reactions further predicted that an n-heptane/toluene fuel with the same RON as the corresponding primary reference fuel had higher resistance to auto-ignition in HCCI combustion for lower intake
temperatures and higher intake pressures. However, for higher intake temperatures and lower intake pressures the
n-heptane/toluene fuel and the PRF fuel had similar combustion phasing.
2004 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
Keywords: HCCI; Homogeneous charge compression ignition; Auto-ignition; Fuel chemistry; Primary reference fuels;
n-heptane; Toluene; Co-oxidation; CHEMKIN
1. Introduction
Homogeneous charge compression ignition
(HCCI) combustion, first studied over 20 years ago
[1,2], is a combustion process which utilizes a (more
or less) homogeneous fuel/air mixture. Combustion is
initiated by auto-ignition of the usually very fuel-lean
* Corresponding author. Fax: +46-8-696-0007.
mixture. It offers a number of benefits over conventional spark-ignition and diesel engines, such as much
lower NOx emissions, higher combustion efficiency
at part load than its SI counterpart, and zero particulates [3,4]. A disadvantage is the relatively high
emissions of unburned hydrocarbons [5], the sources
being quenching wall boundary layers [6] and crevice
regions [7,8].
Unlike the diesel and spark-ignition engines,
where the combustion is directly controlled by the
0010-2180/$ see front matter 2004 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.combustflame.2004.11.009
268
region. Leppard suggested that in the MON test condition, the NTC region dominates the chemistry of
PRF fuels and reactions slow down, making PRF fuels relatively more resistant to knock compared to
fuels containing aromatics and olefins. In the RON
test condition the NTC chemistry becomes less important so that the PRF fuels lose the advantage of
higher resistance to auto-ignition compared to nonPRF fuels. Hence a non-PRF fuel has low MON and
high RONit is relatively more resistant than a PRF
fuel to auto-ignition in the RON test than in the MON
test.
In this work we have studied the auto-ignition of
fuel blends including mixtures of primary reference
fuels and n-heptane/toluene. Emphasis is on detailed
chemistry modeling and a simpler single-zone physical model of the engine is used. The chemistry models
are validated against shock-tube and rapid compression machine data and then used to simulate HCCI
experiments. Our goal is to gain further insight into
the modeling of complex fuel chemistry of fuel blends
that is necessary in order to understand the autoignition process. For that purpose we have especially
investigated the role of co-oxidation between the individual fuel components. An attempt is made to understand why the same non-PRF fuel behaves like different PRF fuels under different conditions in terms of
auto-ignition chemistry.
2. Experimental procedure
The experiments were conducted in a single cylinder engine based on a Scania D12 model, as part of
the Green Car project involving the Swedish government, Volvo, Scania CV, and Shell. The engine
details and fuels studied are given in Tables 1 and 2,
respectively, and the experimental procedure is summarized below. In a typical experiment the engine oil
and water temperatures are brought up to the operating values, 80 C for oil and 90 C for water. The
Table 1
Details for the single-cylinder engine based on a Scania D12
model
Compression ratio
Bore
Stroke
Connecting rod length
Number of valves
Inlet valve opening (IVO)
Inlet valve closing (IVC)
Maximfum inlet valve lit
Exhaust valve opening (EVO)
Exhaust valve closing (EVC)
Maximum exhaust valve lift
16.7
127 mm
154 mm
255 mm
4
367 CAD ATC
581 CAD ATC
14.8 mm
121 CAD ATC
349 CAD ATC
14.8 mm
269
intake boost pressure and temperature and the engine speed are fixed and the fuel is introduced until
auto-ignition takes place as indicated by the pressure
signal and the increase in power delivered by the engine. The fuel quantity is adjusted until the required
normalized air fuel ratio, , is achieved. is the inverse of the fuel/air equivalence ratio, . Once the
engine operating characteristics have stabilized at the
required levels a hundred pressure cycles are acquired
and stored for later analysis. This is repeated for different fuels under the same operating conditions
Table 2
Fuels used and their properties
3. Theoretical discussion
Fuel
A
B
C
D
i-C8 H18
%vol
n-C7 H16
%vol
94
84
6
16
25
35
-CH3
%vol
RON
MON
75
65
94
84
82.6
73.2
Table 3
Operating conditions
OP1
OP2
OP3
OP4
Engine
speed, rpm
Intake air
temperature,
C
Intake
pressure,
bar (abs)
900
1200
900
1200
40
40
120
120
2
2
1
1
4.0
5.5
3.5
3.0
270
(1)
where sensitivity
S = RON MON.
(2)
S is a measure of the difference in auto-ignition chemistry between PRF and the non-PRF fuel being considered, on moving from the MON to the RON test
conditions; for a PRF fuel, S is zero. For a non-PRF
fuel, the OI is the octane number of the PRF fuel with
the equivalent auto-ignition characteristics at the particular condition. K is a constant depending on the
operating conditionsit is not a property of the fuel.
From Fig. 1 it can be seen that for both knock and
HCCI, K decreases as we move to a lower polytrope,
i.e., as the temperature for a given pressure decreases.
K is positive or negative depending on whether the
temperature for a given pressure is higher or lower
than the condition where the auto-ignition quality is
determined by RONin Fig. 1, condition OP3 in
HCCI tests and the RON line for knock tests. The
two lines do not coincide probably because of differences in mixture strengthK is probably a function
of both the operating polytrope and , for > 0.3.
HCCI experiments show that K depends primarily on
the temperature at a given pressure [26,27] but there
is some evidence that K also increases as increases
from 0.3 to 0.4 [26].
HCCI engines can be run at different operating
conditions such that K varies widely. Under condition
OP1, with a high intake pressure, Fuel D, a mixture
of 65% volume toluene and 35% volume n-heptane,
with 84 RON and 73 MON was more resistant to
auto-ignition than iso-octane, PRF100, so that K was
1.6. However an HCCI engine can be run in such
a way that K > 1 (see Fig. 1), by increasing the intake temperature [26]. In such cases, Fuel D would
match a PRF fuel of an octane number less than 73.
Thus compared to PRF 84, Fuel D becomes more or
less resistant to auto-ignition depending on whether
the polytrope is below or above the OP3 polytrope.
In practice, compared to a PRF fuel, a sensitive fuel
(with aromatics, olefins, oxygenates) becomes more
(3)
and
R1 OO + RH = R1 OOH + R ,
(4)
where RH is the fuel, R is alkyl radical after H abstraction, and ROO an alkyl-peroxy radical formed
when the alkyl radical reacts with molecular oxygen.
If co-oxidation reactions are neglected undue restrictions are introduced in the reaction paths for a
mixture of two fuels compared to the reactions of
each of the two fuels alone. This may not be immediately obvious but the following simple example
clearly shows why this is so. Let us assume that two
reactants, A and B, both can react to form C:
2A C;
2,
r1 = k1 CA
(5)
2B C;
2.
r2 = k2 CB
(6)
r3 = k3 CA CB .
(7)
If we consider a mixture of A and B with total concentration CF = CA + CB the reaction rate would
become
2 + k C2 + k C C
r = (r1 + r2 + r3 ) = k1 CA
2 B
3 A B
2
2
2
= k1 + k2 (1 ) + k3 (1 ) CF ,
(8)
where
=
CA
.
CF
(9)
(10)
Hence
k3
2
2
2
k1 = k1 + 1 2 + +
,
k1
(11)
and
1 = (2 n) 2 (2 n) + 1,
(12)
where
k
n= 3.
k1
(13)
The only value that can satisfy Eq. (12) for all
values of is n = 2. The explanation of this mathematical fact that we have to count the third reaction
with double reaction rate is that reaction (7) gets reactants from two different populations of molecules
while the two first reactions get both reactant molecules from the same population.
A more comprehensive discussion more directed
to co-oxidation kinetics can be found in [28], which
treats low-temperature autoxidation of hydrocarbons
and olefins. In that context the importance of cooxidation reactions for the chemical kinetics of the
autoxidation of mixtures is well established. More recent work can for example be found in [2931] where
co-oxidation reactions are used in pseudo-detailed
mechanisms used to describe low-temperature oxidation of hydrocarbons and antioxidants.
4. Modeling procedure
A single-zone modeling approach (no heat transfer, crevices, and charge inhomogeneities) is used.
The usefulness of the single-zone assumption is in
providing an estimate of ignition delay time as a function of thermodynamic conditions in the combustion
chamber [32].
271
272
Fig. 2. Calculated ignition-delay times for primary reference fuel mixtures at constant volume compared with experimental
shock-tube results from Fieweger et al. [36]. p = 40 bar, = 1.0. The LLNL mechanism with added co-oxidations reactions in
Appendix A improves the prediction for PRF80.
the HCCI-engine are simulated and the impact of cooxidation reactions is discussed.
5.1. Validation of reaction mechanisms
The added co-oxidation reactions for the PRF
mechanism [15,16] together with their rate constants
are listed in Appendix A. Based on [17] and similar
reactions found for n-heptane in the LLNL mechanism (e.g., nc7h16 + c7h15-1 = c7h15-2 + nc7h16)
an activation barrier of 1014 kcal/mol was taken
for the hydrogen abstraction reactions from isooctane by heptyl radicals (reactions 42394254 in
Appendix A). For co-oxidation involving alkylperoxides abstracting hydrogen atoms from iso-octane and
n-heptane (reactions 42554286) a similar activation
energy between 15 and 20 kcal/mol was assumed as
for reactions found in the LLNL mechanism for nheptane and iso-octane (e.g., nc7h16 + c7h15o2-2 =
c7h15-3 + c7h15o2h-2 and ic8h18 + ac8h17o2 =
dc8h17 + ac8h17o2h). Also logical activation energies that accounted for the relative strength of
primary, secondary, and tertiary CH bonds were
adopted in the co-oxidation reactions. Consequently,
as tertiary bonds are weakest, these CH bondbreaking reactions were faster than secondary and
primary ones. Finally co-oxidation reactions involving two other isomers of heptane were assumed;
2,4-dimethylpentane (denoted c7h162-4) and 2,2-
273
Fig. 3. Predicted ignition-delay times for primary reference fuels as a function of octane number in a rapid compression machine.
p = 1 bar, T = 318 K, = 2.5. Filled rings: experimental results from Tanaka et al. [10]. Solid line: LLNL mechanism with
added co-oxidations reactions in Appendix A. Dashed line: LLNL mechanism [16].
The pressure and the average cylinder temperature have been measured in HCCI experiments for
different fuels of different chemistries [25]. However
in engines, the charge is not truly homogeneous [39]
primarily because the fresh charge mixes with hot
residual gases from the previous cycle. Hence autoignition should start at these hot spots [40] whose
temperature would be higher than the average, bulk
temperature. The difference, T , between the temperature of the hot spot and the bulk temperature
should be larger, the cooler the intake charge. Hence
we assume that T at 99 before top dead center,
our initial point in the calculation is 45 K for OP1
and 25 K for OP3. These chosen values for T are
arbitrary but without such an increment on the measured temperature, especially Fuel A (PRF 94) and
Fuel D could not be made to ignite at OP1 and OP2
even when they actually did ignite in experiments.
In Figs. 4 and 5 predicted and experimental pressures are plotted against crank angle for Fuels A, B
and C, D, respectively, for operating condition OP3
(high intake temperature/low intake ressure). The corresponding curves for Fuels B and D at operating condition OP1 (low inlet temperature/high inlet pressure)
are shown in Fig. 6. Both simulations with and without added co-oxidation reactions in Appendices A
and B are shown. Obviously the single-zone model
overpredicts the pressure rise during auto-ignition but
this is of minor importance in this work where the
time of auto-ignition is more relevant.
274
Fig. 4. Experimental and calculated pressures for Fuels A and B as a function of crank angle for operating condition OP3 (low
intake pressure/high intake temperature). Initial temperature and pressure at the start of calculations (99 before top dead center)
is 472 K, 1.74 bar for Fuel B and 455 K, 1.37 bar for Fuel A, respectively. ATDC, after top dead center.
Fig. 5. Experimental and calculated pressures for Fuels C and D as a function of crank angle for operating condition OP3 (low
intake pressure/high intake temperature). Temperature and pressure at the start of calculations (99 before top dead center) is
472 K and 1.74 bar, respectively.
275
Fig. 6. Experimental and calculated pressures for Fuels B and D as a function of crank angle for operating condition OP1 (high
intake pressure/low intake temperature). Temperature and pressure at the start of calculations (99 before top dead center) is
415 K and 3.34 bar, respectively.
276
Fig. 7. Experimental and calculated heat release rate (J/deg) for Fuels B and D as a function of crank angle for operating
condition OP3 (low intake pressure/high intake temperature). Temperature and pressure at the start of calculations (99 before
top dead center) is 472 K and 1.74 bar, respectively.
(14)
Reaction (14) can begin at relatively low temperatures since the CH bonds of the methyl group
in toluene have unusually low bond dissociation energy [41]. As the radical pool builds by the lowtemperature oxidation of n-heptane, the reaction
TOLUEN + OH = PHCH2 + H2 O
(15)
starts to dominate the toluene consumption and benzyl production. This in turn will inhibit n-heptane oxidation as toluene competes with n-heptane for OH
radicals. Benzyl radicals, the product in reaction (15),
are less reactive compared to heptyl radicals produced by n-heptane and OH. Note that there is a rapid
partial conversion at an early CAD, and then there
is a plateau in toluene conversion combined with a
277
Fig. 8. Experimental and calculated heat release rate (J/deg) for Fuels B and D as a function of crank angle for operating
condition OP1 (high intake pressure/low intake temperature). Temperature and pressure at the start of calculations (99 before
top dead center) is 415 K and 3.34 bar, respectively.
Fig. 9. Calculated conversion for individual fuel components of Fuel B (ic8h18 and nc7h16) as a function of crank angle for
OP3 and OP1.
278
Fig. 10. Contribution of different reactions to overall rate of production for the c7h15-2 radical: Fuel B, OP1, Interval 9920
crank angles before top dead center.
Fig. 11. Calculated conversion for individual fuel components of Fuel D (nc7h16 and c6h5ch3) as a function of crank angle for
OP3.
ical while producing a reactive heptyl. The following reactions of heptyl will then produce OH that in
turn will convert more toluene into benzyl, according to reaction (15), leading to the higher initial con-
279
Fig. 12. Calculated conversion for individual fuel components of Fuel D (nc7h16 and c6h5ch3) as a function of crank angle for
OP1.
(16)
rate expressions for the gas-phase reactions. The firstorder sensitivity coefficient matrix is then defined as
wj,i =
,
i
(17)
where the indices j and i refer to the dependent variables and reactions, respectively.
Differentiating Eq. (17) with respect to the preexponentials Ai yields
dwj
F j
F
=
wj,i +
.
dt
(18)
In DASPK, the sensitivity equations are solved simultaneously with the dependent variables of the solution itself. The Jacobian matrix F / in Eq. (18)
is exactly the one that is required by the backwardsdifferentiation formula method in solving the original
model problem, so it is readily available for sensitivity
computation. The raw sensitivity coefficients are normalized in the form of logarithmic derivates to make
them more useful, e.g., for species mass fractions
ln Yk
i Yk
(19)
=
.
ln i F
Yk i F
Although the gas-phase species solution variables
are mass fractions, the sensitivity coefficients are
computed in terms of mole fractions as follows,
Kg
i Xk
1 Yk
i Yk
=
i W
,
Xk i F
Yk i F
W i F
j =1 j
(20)
280
Fig. 13. Contribution of different reactions to overall rate of production for the benzyl (PHCH2 ) radical: Fuel D, OP1, interval
9928 crank angles before top dead center.
Fig. 14. Normalized first-order sensitivity coefficients of the OH radical with respect to preexponentials for Fuel B at OP1. 20
CA ATDC, T = 826 K, p = 46.5 bar.
281
Fig. 15. Normalized first-order sensitivity coefficients of the OH radical with respect to preexponentials for Fuel D at OP1. 28
CA ATDC, T = 751 K, p = 31.3 bar.
ity calculation was done between 22 and 20 crankangles before top dead center and the position shown
in Fig. 14 is 20 before top dead center. It can be noted
that co-oxidation reactions are among the most sensitive for building up the radical pool.
In Fig. 15 shows a bar plot of normalized firstorder sensitivity coefficients of the OH radical with
respect to preexponentials for Fuel D at OP1. The sensitivity calculation was done between 30 and 28 crank
angles before top dead center and the position shown
in Fig. 15 is 28 before top dead center. It can be
noted that co-oxidation reactions 14 in Appendix B
are among the most sensitive for building up the radical pool as they transform benzyl radicals to the more
reactive heptyl radicals. This also supports the discussion above that co-oxidation reactions lead to an
increased OH production and a faster fuel conversion.
5.5. An attempt at chemical explanation of the
co-oxidation effects
The ignition delays of Fuels B (PRF84) and D
(toluene/n-heptane, RON84) in the HCCI experiments are almost equal at OP3 (low intake pressure,
high intake temperature) while Fuel B ignites much
earlier than Fuel D at OP1 (high intake pressure, low
intake temperature). Thus their ignition delays do not
correspond to their RON or MON. This raises the
question if co-oxidation reactions could be important
for this behavior. The following discussion summarizes our attempt to answer this question.
n-heptane has 10 secondary carbonhydrogen
bonds and 6 primary ones. Iso-octane has one tertiary carbonhydrogen bond, two secondary carbon
hydrogen bonds, and 15 primary carbonhydrogen
bonds. Toluene has three primary carbonhydrogen
bonds and five carbonhydrogen bonds on the aromatic nucleus. Due to the increasing bond dissociation energies free radicals abstract hydrogen most
easily from the tertiary carbonhydrogen bonds, less
easily from the secondary bonds, and least easily from
the primary bonds in iso-octane and n-heptane. The
abstraction of hydrogen from the aromatic nucleus
in toluene is very difficult and may almost be neglected while abstraction of hydrogen from the three
primary carbonhydrogen bonds would be the easiest case according to the bond dissociation energy
that is 5 kcal/mol less for a primary bond in toluene
than for a tertiary carbonhydrogen bond in a paraffin.
However, the benzyl radicals formed after hydrogen
abstraction from toluene are thermally stable due to
electron delocalization and their reaction with oxygen
at auto-ignition temperatures is thermodynamically
less favored. They will preferably take part in radicalradical reactions [41]. The radicals formed from isooctane and n-heptane, on the other hand, will have
numerous reaction paths available. However, some of
the reaction paths in n-heptane oxidation and to a less
282
Appendix A
Rate constants for added co-oxidation reactions between n-heptane (nc7h16) and iso-octane (ic8h18) to the LLNL mechanism
[15,16]
4239.
4240.
4241.
4242.
4243.
4244.
4245.
9.00E+11
2.00E+11
1.00E+11
6.00E+11
9.00E+11
2.00E+11
1.00E+11
0.0
0.0
0.0
0.0
0.0
0.0
0.0
13500.0
11200.0
9000.0
13500.0
14500.0
11200.0
10000.0
(continued on next page)
283
Appendix A (continued)
4246.
4247.
4248.
4249.
4250.
4251.
4252.
4253.
4254.
4255.
4256.
4257.
4258.
4259.
4260.
4261.
4262.
4263.
4264.
4265.
4266.
4267.
4268.
4269.
4270.
4271.
4272.
4273.
4274.
4275.
4276.
4277.
4278.
4279.
4280.
4281.
4282.
4283.
4284.
4285.
4286.
4287.
4288.
4289.
4290.
4291.
4292.
4293.
4294.
4295.
4296.
4297.
4298.
4299.
4300.
4301.
4302.
4303.
6.00E+11
9.00E+11
2.00E+11
1.00E+11
6.00E+11
9.00E+11
2.00E+11
1.00E+11
6.00E+11
3.15E+13
2.10E+13
2.10E+13
1.05E+13
3.15E+13
2.10E+13
2.10E+13
1.05E+13
3.15E+13
2.10E+13
2.10E+13
1.05E+13
3.15E+13
2.10E+13
2.10E+13
1.05E+13
1.21E+14
1.21E+14
1.21E+14
1.21E+14
3.06E+13
3.06E+13
3.06E+13
3.06E+13
1.53E+13
1.53E+13
1.53E+13
1.53E+13
8.07E+13
8.07E+13
8.07E+13
8.07E+13
9.00E+11
2.00E+11
1.00E+11
6.00E+11
9.00E+11
2.00E+11
1.00E+11
6.00E+11
9.00E+11
2.00E+11
1.00E+11
6.00E+11
1.21E+14
1.21E+14
1.21E+14
5.60E+13
5.60E+13
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
14500.0
14500.0
11200.0
10000.0
14500.0
14500.0
11200.0
10000.0
14500.0
17500.0
15500.0
15500.0
15500.0
17500.0
15500.0
15500.0
15500.0
17500.0
15500.0
15500.0
15500.0
17500.0
15500.0
15500.0
15500.0
18500.0
18500.0
18500.0
18500.0
15500.0
15500.0
15500.0
15500.0
14500.0
14500.0
14500.0
14500.0
18500.0
18500.0
18500.0
18500.0
13500.0
11200.0
9000.0
13500.0
14500.0
11200.0
10000.0
14500.0
14500.0
11200.0
10000.0
14500.0
18500.0
18500.0
18500.0
15500.0
15500.0
284
Appendix A (continued)
4304.
4305.
4306.
4307.
4308.
4309.
4310.
4311.
4312.
4313.
4314.
4315.
4316.
4317.
4318.
4319.
4320.
4321.
4322.
4323.
4324.
4325.
4326.
4327.
4328.
4329.
4330.
4331.
4332.
4333.
4334.
4335.
4336.
4337.
4338.
4339.
4340.
4341.
4342.
4343.
4344.
4345.
4346.
4347.
4348.
4349.
4350.
4351.
4352.
4353.
4354.
4355.
4356.
4357.
4358.
4359.
4360.
4361.
5.60E+13
2.80E+13
2.80E+13
2.80E+13
8.07E+13
8.07E+13
8.07E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
6.30E+13
9.00E+11
2.00E+11
1.00E+11
6.00E+11
9.00E+11
2.00E+11
1.00E+11
6.00E+11
9.00E+11
2.00E+11
1.00E+11
6.00E+11
9.00E+11
2.00E+11
1.00E+11
6.00E+11
1.17E+14
1.17E+14
1.17E+14
1.17E+14
2.60E+13
2.60E+13
2.60E+13
2.60E+13
2.60E+13
2.60E+13
2.60E+13
2.60E+13
3.90E+13
3.90E+13
3.90E+13
3.90E+13
2.52E+14
2.52E+14
2.52E+14
2.52E+14
2.60E+13
2.60E+13
2.60E+13
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
15500.0
14500.0
14500.0
14500.0
18500.0
18500.0
18500.0
17500.0
15500.0
16500.0
17500.0
15500.0
16500.0
17500.0
15500.0
16500.0
17500.0
15500.0
16500.0
13500.0
11200.0
9000.0
13500.0
14500.0
11200.0
10000.0
14500.0
14500.0
11200.0
10000.0
14500.0
14500.0
11200.0
10000.0
14500.0
17500.0
17500.0
17500.0
17500.0
15500.0
15500.0
15500.0
15500.0
15500.0
15500.0
15500.0
15500.0
17500.0
17500.0
17500.0
17500.0
18500.0
18500.0
18500.0
18500.0
15500.0
15500.0
15500.0
285
Appendix A (continued)
4362.
4363.
4364.
4365.
4366.
4367.
4368.
4369.
4370.
2.60E+13
1.30E+13
1.30E+13
1.30E+13
1.30E+13
1.68E+14
1.68E+14
1.68E+14
1.68E+14
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
15500.0
14500.0
14500.0
14500.0
14500.0
18500.0
18500.0
18500.0
18500.0
kf = AT n exp(E/RT ).
A units mol cm s K; E units cal/mol.
Appendix B
Rate constants for added co-oxidation reactions between n-heptane (n-C7H16) and toluene (-CH3) to merged neat mechanisms
for individual fuels [16,35]
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
7.50E+11
5.00E+11
5.00E+11
2.50E+11
3.00E+12
3.00E+12
3.00E+12
3.00E+12
3.00E+12
3.00E+12
3.00E+12
3.00E+12
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
8000
7000
7000
7000
12000
12000
12000
12000
12000
12000
12000
12000
kf = AT n exp(E/RT ).
A units mol cm s K; E units cal/mol.
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