Fuel 184 (2016) 836845

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Full Length Article

Laminar flame characteristics and kinetic modeling study

of methanol-isooctane blends at elevated temperatures
Qianqian Li , Weijie Zhang, Wu Jin, Yongliang Xie, Zuohua Huang
State Key Laboratory of Multiphase Flow in Power Engineering, Xian Jiaotong University, Xian, Peoples Republic of China

h i g h l i g h t s

Laminar flame speeds and Markstein lengths of methanol-isooctane blends were measured in a constant volume vessel.

Effects of methanol addition into isooctane on laminar flame speed and Markstein length were illustrated.

An accurate chemical model was proposed for methanol-isooctane blends.

Laminar flame speed directly correlates to H concentration.

a r t i c l e

i n f o

Article history:
Received 3 May 2016
Received in revised form 21 July 2016
Accepted 22 July 2016
Available online 27 July 2016
Keywords:
Methanol
Isooctane
Laminar flame speed
Kinetic modeling
Markstein length

a b s t r a c t
Laminar flame speeds of methanol-isooctane blends were experimentally determined using the spherically propagating flame in a constant volume chamber at two initial temperatures (363 and 393 K), different blending ratios of methanol in liquid volume (0%, 20%, 40%, 80%, 100%), and over equivalence ratios
of 0.71.6. Nonlinear methodology was employed to remove the stretch effect in the data processing.
Results indicate that laminar flame speeds of methanol flame reach the peak at equivalence ratio around
1.2 and that of isooctane at equivalence ratio around 1.1. For the mixtures with less than 40% methanol,
laminar flame speeds show moderate increase at all equivalence ratios. However, further increasing
methanol addition will greatly accelerate laminar flame speeds at rich mixture sides but give slight
change at lean mixture sides. Markstein length shows an increase tendency with the methanol addition
at the equivalence ratios larger than a critical value while Markstein length gives a decrease tendency at
the equivalence ratios smaller than the critical value. The critical equivalence ratio is between 1.2 and 1.3.
Among the thermal effect, diffusive effect and kinetic effect, the kinetic effect was found to be the major
factor bringing the variation of laminar flame speed with the variation of blending ratio. A kinetic model
(IM model) was developed on the basis of the isooctane model of Chaos et al. (2007). The IM model shows
good prediction on measured laminar flame speeds under all conditions. Reaction pathway reveals that
the HCO and H productions are promoted while the productions of stable species are inhibited in the case
of methanol addition into the isooctane at rich mixture sides, resulting in the laminar flame speed
enhancement. These behaviors are verified from the sensitivity analysis and the concentrations of the
reactive radicals.
2016 Elsevier Ltd. All rights reserved.

1. Introduction
Methanol is recognized as one of the promising alternative
fuels. It can be derived from the natural gas, coal, biomass and even
the garbage [2]. Moreover, it is environment friendly and has high
octane number [25]. However, it still has some disadvantages like

Corresponding authors at: State Key Laboratory of Multiphase Flow in Power

Engineering, Xian Jiaotong University, Xian 710049, Peoples Republic of China.
E-mail addresses: qianqianli@mail.xjtu.edu.cn (Q. Li), zhhuang@mail.xjtu.edu.cn
(Z. Huang).
http://dx.doi.org/10.1016/j.fuel.2016.07.087
0016-2361/ 2016 Elsevier Ltd. All rights reserved.

cold starting problem and low energy density, restricting its practical application of pure methanol in engines. Therefore, methanol
is extensively utilized in engines as the blends with gasoline. Isooctane is regarded as gasoline surrogate and reference fuel and has
single component. Therefore, understanding of combustion characteristics of methanol-isooctane blends has the reference to
methanol-gasoline blends.
Laminar flame speed is a fundamental property to characterize
the combustion process of the mixture and determine turbulent
flame speed [6]. Moreover, it is widely used to validate chemical
kinetic models. Laminar flame speeds of methanol-air and

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Q. Li et al. / Fuel 184 (2016) 836845

methanol-isooctane blends and validated against the measured

laminar flame speeds. On the basis of the proposed model, reaction
pathway and sensitivity analyses were conducted to clarify the role
of key intermediate species and get the insight into the combustion
chemistry of the methanol-isooctane blends.

2. Experimental apparatus and data processing

2.1. Experimental apparatus
In this study, the spherically propagating flame was examined
in a constant volume chamber. The apparatus will be briefly
described here with the details seen in literatures [9,30]. The combustion chamber is cylindrical with inner diameter of 180 mm. Initial temperatures of 363 and 393 K were achieved by heating the
chamber with a surrounding heating-tape. The temperature was
monitored by an S-type thermocouple located inside the chamber
with the accuracy of 2 K. The pressure was calibrated by the pressure transducer and transmitter with the relative pressure deviation of 1%. For each experiment, the chamber was vacuumed at
the beginning. The liquid fuel (methanol and isooctane) was
injected into the chamber using micro syringes. At least five
5 min was awaited prior to the ignition to ensure the full evaporation. Then the air composed of 21% O2 and 79% N2 was introduced
into the chamber. The mixture was ignited with the electrodes
located in the chamber center and the flame propagation was
recorded by a Phantom high-speed camera.

0.7

(a)

methanol

0.6

Pu = 0.1 MPa

Su0/ ms-1

0.5
0.4
Present data, 363 K
Veloo et al., 343K [11]
Veloo et al., corrected-363 K

0.3
0.2

Metghalchi et al., 363 K [16]

0.1

Liao et al., 363 K [40]

Saeed et al., 363 K [41]

0.0

Egolfopoulos et al., 368K [42]

-0.1

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Equivalence ratio f
0.6

(b)
iso-octane

0.5
0.4

Su0/ ms-1

isooctane-air mixtures at wide initial conditions were extensively

reported in the previous publications. Mitu et al. [7], Katoch et al.
[8], and Zhang et al. [9] all determined the laminar flame speeds
of methanol flames with the constant volume chamber, covering
the initial temperatures of 323650 K and pressures of
0.10.5 MPa. Egolfopoulos et al. [10,11] measured the laminar
flame speeds of methanol and isooctane flames in a counterflow
configuration. Results indicated that the data reach the peak
around 1.2 for methanol flame and around 1.1 for isooctane flame.
Similar behavior was observed by Beeckmann et al. [12,13] and
Sileghem et al. [14]. Ryan et al. [15] and Metghalchi et al. [16] measured the laminar flame speeds of methanol and isooctane flames
in a constant volume chamber, and found that the methanol flame
exhibits faster flame speed than the isooctane flame. However, limited data were reported for the laminar flame speeds of the
methanol-isooctane blends. Broustail et al. [17,18], Zhang et al.
[19] and Lipzig et al. [20] experimentally determined the laminar
flame speeds of ethanol-isooctane and n-butanol-isooctane blends
at different initial temperatures and pressures. They concluded
that alcohol-isooctane blends propagate faster than isooctane but
slower than alcohol. Gulder et al. [21] reported the laminar flame
speeds of the methanol-isooctane blends at 300 K and atmospheric
pressure. They observed the decrease of laminar flame speed when
adding the methanol into the isooctane. Without the available
kinetic model, they suggested that methanol addition suppresses
the overall reactivity by producing CH2O and consuming reactive
intermediates. Sileghem et al. [14] determined the laminar flame
speeds of the blends of 75% methanol and 25% isooctane with
the heat flux method to investigate the mixing rule. Beeckmann
et al. [13] measured the laminar flame speeds of methanol, isooctane and the blend of 90% isooctane and 10% methanol at 373 K
and 1.0 MPa. Results indicated that the methanol-isooctane blend
exhibits lower values than methanol and approximate values with
pure isooctane, which contradicts with the result reported by Gulder et al. [21]. All the data mentioned above have been summarized in Table S1 in the Supplementary materials for clarity.
Accurate chemical kinetic model facilitates the understanding
of combustion phenomenon. Kinetic studies on methanol in the
early time [22,23] were based on the simple structure. These models were later adopted as the base to construct those of higher alcohols and heavy hydrocarbons like isooctane. Li et al. [22] developed
a detailed high temperature model for CO, CH2O, CH3OH which
was validated against a large numbers of experimental datasets.
This model was then adopted as the base model of the DME model
developed by Zhao et al. [24]. Curran et al. [25] proposed a detailed
model of isooctane including the methanol reactions. This model
was subsequently reduced by Lu and Law [26] and PepiotDesjardins and Pitsch [27], respectively. However, PepiotDesjardinss model exhibited significant over-predictions on the
laminar flame speed of isooctane while Lus model was not validated against the laminar flame speed. Chaos et al. [1] developed
a detailed PRF model, which has been validated against several
experimental datasets including the laminar flame speeds of isooctane. To our knowledge, limited kinetic study was reported on the
methanol-isooctane blends. Jerzembeck et al. [28] derived a
reduced model on the basis of the LLNL detailed model for PRF
[29], which unfortunately yields over-predictions on the laminar
flame speeds of methanol-isooctane blends [13].
The objective of this study is to provide the laminar flame
speeds and investigate the chemical kinetic properties of the
methanol-isooctane blends. Specifically, laminar flame speeds of
methanol-isooctane blends were determined with spherically
propagating flame at initial temperatures of 363 and 393 K, varied
methanol blending ratios (0, 20%, 40%, 80%, 100%) and equivalence
ratios of 0.71.6. An improved model was proposed for the

Pu = 0.1 MPa

0.3

Present data, 363 K

0.2

Baloo et al., 363 K [44]

Bradley et al., 358 K [45]

0.1

Kumar et al., 360K [46]

Ma et al., 363 K [47]

0.0
0.6

0.8

1.0

1.2

1.4

1.6

Equivalence ratio f
Fig. 1. Laminar flame speeds of methanol and isooctane-air mixtures from different
groups at 0.1 MPa.

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Q. Li et al. / Fuel 184 (2016) 836845

2.2. Data processing

S0u;RCFS S0u;Exp 0:82S0u;Exp

With the schlieren pictures recorded by the camera, the flame

radius history, rf(t), was acquired. The stretched flame speed can
be deduced through the equation of Sb drdtf t. To remove the
stretch effect on the flame speed, both linear and nonlinear
methodologies were derived in the past. Nonlinear expression of
Frankel and Sivashinsky [31,32], Sb S0b  S0b Lb  2=r f , was
employed here, where Lb is Markstein length of the burned mixture
representing the sensitivity of laminar flame speed to the stretch
rate, and 2=r f is linked to the stretch rate j through
j 2=rf drf =dt. The nonlinear extrapolation yielding the
unstretched flame propagation speed was shown in Fig. S1 in the
Supplementary materials. On the basis of mass conservation across
the flame front, laminar flame speed is therefore calculated by
S0u qb S0b =qu , where qu and qb are the densities of the unburned
and burned mixtures, respectively. Moreover, the adiabatic temperature (Tad) at various initial conditions was determined based
on the thermal equilibrium theory.
An uncertainty in the determination of laminar flame speed
measurement does exist. Efforts were made to avoid the effect of
ignition and vessel confinement by using the flame radii between
8 and 22 mm to do data processing. Cracks may be generated along
with ignition, but it was identified to influence the measurement
accuracy little. The radiation-induced uncertainty was corrected
with a correlation derived by Yu et al. [33],

dS0u

r
 2 
2
BS0u t1a=2 mrS0u

where t 1a=2 m is the students t value at the freedom degrees of m

and 95% confidence interval; rS0u represents the standard deviation
of S0u . BS0u is the total bias uncertainty of the determination methodology and can be estimated through the following equation,

BS0u

v
!2
u n
uX @S0 x
u i
t
ui
@xi
i1

here xi is the factor affecting the accuracy of measurement and ui is

the deviation of the factor. The detailed description on deducing the
total bias uncertainty has been given in the literatures [35,36]. With
this method, the total bias uncertainty was estimated to be
1.32 cm s1. The standard deviation, rS0u , arising from data pro-

4
Tu = 393 K

(a)
0.6

0.5

(a)

Pu = 0.1 MPa

0.4

Lb /mm

Su0/ ms-1

!1:14   
0:3
Tu
P
P0
T0

where S0u;RCFS and S0u;Exp respectively represents the radiationcorrected and originally measured laminar flame speed, S0 = 1 cm/s,
T0 = 298 K, and P0 = 0.1 MPa. The uncertainties deduced by other factors are examined as the total uncertainty since they are difficult to
be individually quantified. Here, we adopt the theory Moffat et al.
[34] to evaluate the experimental uncertainty which is given by,

0.7

0.3
M00
0.2
0.1

Pu = 0.1 MPa

0.6

0.8

M80

-2

1.0
1.2
1.4
Equivalence ratio f

-3

1.6

0.6

0.8

0.8

(b)

0.6

Pu = 0.1 MPa

0.5

0.2

Tu = 393 K

0.1

Pu = 0.1 MPa

0.0

0.8

Lb /mm

0.3

M00
M20
M40
M80
M100

1.0
1.2
1.4
Equivalence ratio f

1
0

M00
M20
M40
M80
M100

-1
-2

1.6

Fig. 2. Laminar flame speeds of methanol-isooctane blends at different blending

ratios and initial temperatures. (Symbols: experimental data; Lines: simulations of
IM model).

1.6

Tu = 393 K

0.4

1.0
1.2
1.4
Equivalence ratio f

(b)

0.7

-0.1
0.6

M00
M20
M40
M80
M100

0
-1

M40
M100

-0.1

M20

Tu = 393 K

0.0

Su0/ ms-1

S0u;Exp
S0

-3
0.6

0.8

1.0
1.2
1.4
Equivalence ratio f

1.6

Fig. 3. Measured Markstein length of different methanol-isooctane blends versus

equivalence ratio at 0.1 MPa and two initial temperatures.

839

Q. Li et al. / Fuel 184 (2016) 836845

rf = 5 mm

10 mm

15 mm

20 mm

25 mm

30 mm
M00

M20

M40

M80

M100

Fig. 4. Schlieren images of methanol-isooctane blend-air mixtures at 0.1 MPa, 363 K and different blending ratios of methanol.

2350

(a)

Tad/K

2300
2250

Tu = 363 K

2200

Pu = 0.1 MPa

2150

M00
M20
M40
M60
M80
M100

2100
2050
2000
1950
1900
0.6

0.8

1.0

1.2

1.4

1.6

Equivalence ratio f
2.6

2.9x10-5

(b)

2.8x10-5

-5

Leeff

/ m2 s-1

2.7x10-5
2.6x10

2.5x10-5

Tu = 363 K

2.4x10-5

Pu = 0.1 MPa

2.3x10-5

= 0.8
= 1.4

-5

2.2x10

0.0

0.2

= 1.0
= 1.6
0.4

2.2

Tu = 363 K

2.0

Pu = 0.1 MPa

= 0.8
= 1.0
= 1.2
= 1.4
= 1.6

1.8
1.6
1.4

= 1.2

0 .6

1.2
1.0

-5

2.1x10

(c)

2.4

0.8

Volume fraction of methanol

1.0

0.8

0.0

0.2

0.4

0.6

0.8

1.0

Volume fraction of methanol

Fig. 5. Adiabatic temperatures, thermal diffusivity and effective Lewis number of methanol-isooctane blends versus equivalence ratio at 363 K and 0.1 MPa. (a) Adiabatic
temperature; (b) thermal diffusivity; (c) effective Lewis number.

Q. Li et al. / Fuel 184 (2016) 836845

2.3. Reactor model

Laminar flame speeds of methanol-isooctane blends were simulated with the PREMIX code [37] coupling with CHEMKIN package
[3739]. Initial temperature was set at 363 K and 393 K, and initial
pressure is 0.1 MPa. Blending ratios of methanol in the blends by
volume are 0%, 20%, 40%, 60%, 80%, 100%. Maximum and adaptive
grid points were respectively set at 500 and 200. The adaptive grid
control based on solution gradient and curvature were reduced to
0.02. Moreover, mixture-averaged transport together with soret
effect were taken into account during the simulation process.
3. Results and discussion
3.1. Laminar flame speeds and Markstein lengths
To validate the performance of experimental apparatus, the
measured data were compared with those published in literatures.
Fig. 1a gives the laminar flame speeds of methanol-air mixtures.
Note that present data are radiation-corrected data. The differences between the original and the radiation-corrected data are
less than 1 cm/s, as seen in Fig. S2 in the Supplementary materials.
It is seen present data reach the peak around equivalence ratio of
1.2, which is consistent with the data of Veloo et al. [11] at 343 K
measured by the counterflow flame. Similar behavior was also
reported for the data of Beeckmann et al. [12] at 373 K and
1.0 MPa determined with spherical propagating flame, and the
data of Sileghem et al. [14] at three temperatures (298, 318,
338 K) and 0.1 MPa measured with the heat flux method. The else
data all give their peak values around equivalence ratio of 1.1. Liao
et al. [40], Metghalchi et al. [16] and Saeed et al. [41] obtained the
data in the constant volume chamber. However, they used different methods to deduce the data. Liao et al. [40] adopted the schlieren pictures while Metghalchi et al. [16] and Saeed et al. [41]
utilized the combustion pressure rise. These data are approximate
with present data at lean conditions but lower at rich mixture
sides. It is noted that the measurement generates the approximate
values to the data of Egolfoupoulos et al. [42] at 368 K under both
lean and rich conditions, but yields slightly lower values under the
stoichiometric condition. The data of Veloo et al. [11] at 343 K were
adjusted to be the data at 363 K on the basis of the empirical correlation of S0u  T 1:8
evaluating the effect of 10 K on the laminar
u
flame speed [43]. It is seen the temperature adjusted data agree
well with present data. Fig. 1b plots measured laminar flame
speeds of isooctane-air mixtures along with the data in the publications [4447]. It is seen present data are smaller than the data of
Kumar et al. [46] measured with the counterflow configuration.
The data of Ma et al. [47], Bradley et al. [45], and Baloo et al. [44]
were all determined by the spherical propagating flame and the
stretch was removed with the linear method. It is seen the literature data agree well with present data extrapolated with the nonlinear method at rich conditions, while yield higher values at lean
conditions. This is reasonable for the linear method was identified
to give higher values than the nonlinear method at lean conditions
for isooctane [48].
Fig. 2 shows the radiation-corrected laminar flame speeds of the
blends at two initial temperatures and varied blending ratios with
an experimental uncertainty marked. The original data can be seen
in Fig. S3 in the Supplementary materials. When blending ratio of

methanol is less than 40%, laminar flame speeds give moderate

increase with the increase of methanol addition. However, further
increasing the methanol addition will remarkably increase the
laminar flame speeds at rich mixture side but slightly influence
the ones at lean mixture side. This laminar flame speed enhancement differs to the result from Gulder et al. [21] but agree with
those of Beeckmann et al. [13] and Sileghem et al. [14].
Markstein length is a parameter representing the response of
laminar flame speed to flame stretch and characterizing the flame
instability. Positive value indicates stable flame front while
negative value indicates unstable flame front. Fig. 3 shows the
Markstein lengths of different blends at 0.1 MPa and 363 K. The
results show that there exists a critical equivalence ratio, under
which Markstein length decreases with the addition of methanol
into isooctane. When equivalence ratio is larger than the critical
value, Markstein length shows an increase trend with the increase
of methanol addition. The critical value is between 1.2 and 1.3.
Similar behavior was reported by Zhang et al. [19] in the study of
n-butanol-isooctane blends with close critical value presented.
Additionally, Markstein length decreases with the increase of
equivalence ratio, and this is inherently caused by the non-equal
diffusion of heat and mass. Fig. 4 shows the schlieren images of
methanol-isooctane blends at equivalence ratio of 1.5. It is
observed that cracks appear on the flame front surface and are
developing with the propagation of pure isooctane flame. With
the addition of methanol into the isooctane, the crack number
exhibits a decrease tendency and even no crack appears for pure

0.6

(a)

iso-octane
0.5
0.4

Su0/ ms-1

cessing was approximately 0.32 cm s1. At each condition, 4080

schlieren pictures were utilized for data processing, thus the value
of m was 4080 and the values of t 1a=2 m were obtained. With
Eq. (2), the experimental uncertainty was determined to be approximate 24 cm s1.

T u = 363 K

0.3

P u = 0.1 MPa

0.2

Present data
Chaos et al. [1]
Lu et al. [26]
Pepiot-Desjardins et al. [27]

0.1
0.0

0.6

0.8

1.0
1.2
1.4
Equivalence ratio f

1.6

0.8

(b)
0.7

methanol

0.6

Su0/ ms-1

840

0.5
0.4
0.3
0.2
0.1
0.0

0.6

Tu = 363 K
Pu = 0.1 MPa

0.8

Present data
Chaos et al. [1]
Li et al. [22]
Zhao et al. [24]
Lu et al. [26]
Pepiot-Desjardins et al. [27]

1.0
1.2
1.4
Equivalence ratio f

1.6

Fig. 6. Comparison between the simulated and measured laminar flame speeds for
the isooctane-air and methanol-air mixtures.

841

Q. Li et al. / Fuel 184 (2016) 836845

CH3

(a)

CH2

CH2

H3C

CH3

H3C
CH

H3C

CH2

CH3

99%
99%
99%

CH3

+
CH2

CH CH3

60.3%
68.2%
72.2%

CH3

43.3%
43.0%
43.0%

H3C

H3C

CH3

H3C

CH2

CH2

CH3

CH3

H3C

CH3

CH2

CH3

H3C

CH3
C

CH2
H3C

CH2

H3C

CH3

CH3

1.3%

CH3

CH2

8.9%
8.6% CH3
8.6%

1.4%

CH3
CH3

CH3
H3C

20.1%
16.1% CH3
14.2%

CH3 1.4%

CH2

CH3

CH3

CH3

C8H17(isomers)

11.2%
12.2%
12.3%

CH2

CH3

35.2%
34.8%
34.8%
H3C

CH3

3.6%

H3C

CH

CH3

CH3

H3C

12.0%
9.5%
8.3%

CH3

58.8%
58.9%
59.0%

CH3

CH3

CH3 4.1%

H3C

H3C

41.2%
41.1%
41.0%

CH3

H3C

5.1%

2.5%
2%
1.8%

CH2

CH2

CH2

CH3

CH2

H3C

H3C

CH3

H3C

H3C

H3C

CH3

CH3

CH3
H3C

H3C

H3C

CH3

H2C

CH3

CH3

(b)

CH3

30.5%
20.0%
8.1%
C2H6

9.1%
9.5%
10.6%
CH4

15.4%
15.3%
16.3%
CH2*

23.4%
24.9%
29.1%
CH2O

3.9%
11.6%
21.5%
CH 3O

HCO
H+ CO

CH2OH

23.2%
28.6%
29.5%
76.1%
70.4%
69.6%

CH3OH

Fig. 7. Reaction pathways analyses for pure isooctane (normal text), M40 (bold text) and M80 (italic text) flames at 0.1 MPa, 363 K and equivalence ratio of 1.2.

842

Q. Li et al. / Fuel 184 (2016) 836845

(a)
= 0.8
= 1.0
= 1.4

isooctane
Tu= 363 K
Pu= 0.1 MPa

H+O2<=>O+OH

-0.3

-0.2

-0.1

0.0

0.1

(b)

M40
Tu= 363 K
Pu= 0.1 MPa

H+O2 <=>O+OH

-0.2

-0.1

0.0

0.1

(c)

methanol
Tu= 363 K
Pu= 0.1 MPa

H+O2<=>O+OH

-0.2

-0.1

0.3

0.4

0.5

Laminar flame speed closely links to the properties of thermal,

diffusive and kinetic. Contribution of thermal effect can be characterized by the adiabatic temperature (Tad), and the diffusion effect
can be represented by the thermal diffusivity (a) and Lewis number (Le). High adiabatic temperature and strong diffusion are in
favor of laminar flame speed enhancement. Thermal diffusivity
can be calculated by a q kC p , in which k is conductivity coefficient
u

and Cp is heat capacity. Here, the effective Lewis number was

adopted and calculated by [49],

Leeff
0.6

0.2

0.3

0.4

0.5

0.6

CH3OH+OH<=>CH2OH+H 2O
CH3OH+OH<=>CH3O+H 2O
CH3OH+H<=>CH3O+H2
CH3OH+H<=>CH2OH+H 2
CH3O+M<=>CH2O+H+M
CH 2OH+H<=>CH3+OH
CH 3+H(+M)<=>CH4(+M)
CH 2O+H<=>HCO+H2
HCO+H<=>CO+H 2
HCO+O2<=>CO+HO2
HCO+M<=>H+CO+M
CO+OH<=>CO2+H
H2O2(+M)<=>OH+OH(+M)
HO2+OH<=>H2O+O2
HO2+H<=>OH+OH
HO2+H<=>H 2+O2
H+O2(+M)<=>HO2(+M)
H2O+H2O<=>H+OH+H2O
H2+OH<=>H 2O+H

= 0.8
= 1.0
= 1.4

-0.3

0.2

3.2. Interpretation of the laminar flame speed variation

iC4H8<=>iC4H 7+H
C 3H 6+OH<=>aC3H5+H2O
CH2+O2<=>HCO+OH
C 2H 2+H(+M)<=>C2H3(+M)
C 2H 3+H<=>C2H 2+H 2
C 2H4+H(+M)<=>C2H5(+M)
CH3OH+OH<=>CH3O+H 2O
CH3+H(+M)<=>CH4(+M)
CH3+HO2<=>CH 3O+OH
CH3+O<=>CH2O+H
HCO+H<=>CO+H2
HCO+O2<=>CO+HO2
HCO+M<=>H+CO+M
CO+OH<=>CO2+H
HO2+OH<=>H2O+O2
HO2+H<=>OH+OH
HO2+H<=>H2+O2
H+O2(+M)<=>HO2(+M)
H2+OH<=>H2O+H

= 0.8
= 1.0
= 1.4

-0.3

methanol flame. This indicates that flame instability is suppressed

by methanol addition into the isooctane, which is consistent with
the variation of the Markstein length.

iC4 H8<=>iC 4H7+H

C3H6+OH<=>aC3H5+H2O
C3H6+H<=>aC 3H5+H2
CH2+O2<=>HCO+OH
C2H2+H(+M)<=>C 2H3(+M)
C2H3+O2<=>HCO+CH2O
C2H3+H<=>C2 H2+H 2
C2H4+H(+M)<=>C2H5(+M)
CH 3+OH<=>CH 2*+H2O
CH 3+CH3<=>H+C 2H5
CH 2OH+H<=>CH 3+OH
CH 3+H(+M)<=>CH4 (+M)
CH 3+HO2<=>CH3O+OH
CH 3+O<=>CH 2O+H
HCO+H<=>CO+H 2
HCO+O2<=>CO+HO2
HCO+M<=>H+CO+M
CO+OH<=>CO2+H
H+O2(+M)<=>HO2(+M)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

Fig. 8. Sensitivity analysis of laminar flame speed for isooctane, M40, and methanol
flames at three equivalence ratios. (a) isooctane flame; (b) M40 flame; (c) methanol
flame.

8
~
< LeO 1~/LeF
2/

~
: LeF 1/Le
O
~
2/

/<1
/>1

~ b/  1 and b Ea T ad  T u =RT 0 ; b is Zeldovich

in which /
ad
number; Tu is the initial temperature. LeF and LeO indicates the
Lewis numbers of the fuel and oxidizer, respectively. The Lewis
number of the blending fuel is derived as the average value based
on the mole fractions of the pure fuels. Fig. 5 shows Tad, a and Le
as a function of volume fraction of methanol at 363 K and
0.1 MPa. With the addition of methanol, Tad decreases at the equivalence ratio around 1.0, and a and Le show apparent decrease tendencies. Therefore, the thermal and diffusive parameters all exhibit
negative effect on laminar flame speed variation with the methanol
addition. Moreover, a and Le decrease monotonously with the
increasing equivalence ratio. Tad obtains the maximum value
around equivalence ratio of 1.05 at different blending ratios, and
decreases at richer conditions. This indicates the negative effect of
the thermal and diffusive properties on the laminar flame speed
variation with the mixture richer than 1.05, which does not follow
the equivalence ratio shift of the peak laminar flame speed to the
rich side. Taking account of the analyses above, it is speculated that
the kinetic effect plays a dominant role in the laminar flame speed
variation with the methanol addition into isooctane.
3.3. Model validation and refinements
To well understand the chemical kinetics of the fuel blends, an
accurate model is required. Isooctane model generally embraces
the sub-model of methanol, but the prediction performance on
methanol flame needs to be evaluated. Fig. 6a shows the experimental data and simulations of different isooctane models for pure
isooctane flame at 0.1 MPa and 363 K. A satisfactory agreement is
achieved between the simulations of Chaoss model [1] and the
experimental data at all equivalence ratios. Pepiot-Desjardinss
model [27] yields higher predictions than the experimental data,
while Lus model [26] gives lower predictions. Fig. 6b shows the
comparison between the measured laminar flame speeds and simulations for the pure methanol flame. The isooctane models
[1,26,27] were adopted to do the simulations. Obviously, the isooctane models fail to simulate the methanol flame at both stoichiometric and rich mixtures. This is for several reactions lost in
methanol sub-model. To derive an accurate model for the
methanol-isooctane blends, it is essential to choose a model which
can well predict the pure methanol flame. It is observed the methanol model proposed by Li et al. [22] can successfully reproduce the
laminar flame speeds at lean and rich conditions, but slightly over-

843

Q. Li et al. / Fuel 184 (2016) 836845

predicts by 45 cm/s1 around the stoichiometric ratio. Zhaos

model [24] was developed for dimethyl ether based on the methanol model of Li et al. [22] with several methanol sub-reactions
updated. Zhaos model [24] well predicts the experimental data
at all equivalence ratios with the deviations less than 3 cm/s1.
Thus, the methanol sub-model in Chaos et al. [1] was replaced by
that in Zhaos model [24]. Moreover, the H2-O2 submodel in Zhaos
model was recently updated by Burke et al. [50], and the new H2O2 model of Burke et al. [50] was adopted to increase the model
accuracy. The refined model named IM model was used to do the
further simulations. Simulations of IM model are plotted in Fig. 2
to make a comparison with the experimental data. As expected,
IM model performs fairly well at different blending ratios and initial temperatures. Particularly, the shift of equivalence ratio at
peak values to the rich side with the increase of methanol blending
ratio is accurately captured by the IM model. The model also performs well on predicting the data in literatures [13,28], as seen
in Fig. S4 in the Supplementary Materials.
Fig. 7 depicts the reaction pathway for isooctane, M40 and M80
flames using the IM model at 0.1 MPa, 363 K and equivalence ratio
of 1.2. It is seen that isooctane is initially consumed through H
abstraction reactions and decomposition reactions. Regardless of
the pathways that isooctane goes through, the products are primarily the iC4H7, iC4H8, C3H6, etc. These species are all relatively stable,
working as the retardants for the overall reaction and contributing
the low flame speed of isooctane. Differing to isooctane, methanol is
initially consumed through H abstraction reactions with CH2OH
and CH3O generated, as shown in Fig. 7b. Less CH3O is generated
because of high bond energy between O and H in hydroxyl group

(AOH). Both CH2OH and CH3O go to formaldehyde (CH2O) and generate reactive HCO. HCO will produce an H radical through the reaction of HCO M () H CO M, promoting the overall reactivity.
It is noted that isooctane produces large pool of methyl (CH3).
Examining the productions of CH3, it is found that CH3 not only goes
to CH4 and C2H6 through the chain terminating reactions of
CH3 HM () CH4 M and CH3 CH3 M () C2 H6 M,
but also produces reactive CH2O and CH3O with high branching
ratio. With the increasing blending ratio of methanol, CH2O coming
from CH3OH increases. In addition, more CH3 goes to CH2O and
CH3O while less CH3 goes to C2H6 via the chain terminating
reaction. Consequently, CH2O and HCO generations are highly
promoted, leading to fast laminar flame speed.
Fig. 8 shows the normalized flow rate sensitivity analysis on
laminar flame speed for pure isooctane, M40 and pure methanol
flames at equivalence ratios of 0.8, 1.0 and 1.4. As expected, laminar flame speeds of different flames are mainly sensitive to the
small molecule reactions. In the cases of isooctane and M40, reactions of isobutene and propene are included in the sensitive reactions and exhibit negative sensitivity coefficients, supporting the
reaction pathway analyses. In the case of pure methanol, reactions
of HCO present higher sensitivity coefficients than those in isooctane and M40 flames. This is consistent to the phenomenon that
HCO production is promoted when methanol is added into the
isooctane.
To further support the analysis from the reaction pathway and
sensitivity analyses, the maximum mole fractions of H, OH, CH3
and HCO are shown in Fig. 9 at 0.1 MPa and 363 K for different fuel
blends. In the case of methanol addition into the isooctane, H and

120

(a)
100

80
60
40

Tu= 363 K

20
0
0.6

Pu= 0.1 MPa

0.8

1.0

M00
M20
M40
M60
M80
M100
1.2

Equivalence ratio f

1.4

Maximam mole fraction104

Maximam mole fraction104

120

60
40
20

0.8

1.0

1.2

Equivalence ratio f

1.4

1.6

3.0

(c)
CH3

20
15
10
5

Maximam mole fraction104

Maximam mole fraction104

OH

80

0
0.6

1.6

30
25

(b)
100

(d)
2.5

HCO

2.0
1.5
1.0
0.5

0.6

0.8

1.0

1.2

Equivalence ratio f

1.4

1.6

0.0
0.6

0.8

1.0

1.2

Equivalence ratio f

1.4

1.6

Fig. 9. Maximum concentrations of H, OH, CH3 and HCO radicals for the methanol-isooctane-air mixtures at 0.1 MPa and 363 K. (a) H radical; (b) OH radical; (c) CH3 radical;
(d) HCO radical.

844

Q. Li et al. / Fuel 184 (2016) 836845

OH concentrations are increased and the overall reaction rate is

promoted. Specifically, H radical follows the variation of laminar
flame speed, that is, H radical concentration increases at rich side
and larger increment is presented at higher methanol blending
ratio. Moreover, H concentration also demonstrates the shift of
equivalence ratio to the rich side, confirming the dominant effect
of chemical kinetics on the laminar flame speed variation.
Fig. 9c and d give the maximum mole fractions of CH3 and HCO.
CH3
and
HCO
can
be
respectively
consumed
via
CH3 HM () CH4 M and HCO M () H CO M, changing the H concentration. With the increase of methanol addition,
CH3 concentration is significantly decreased and HCO concentration is increased, leading to the increase of H concentration and
acceleration of reaction. HCO radical follows the trend of H concentration, demonstrating the high sensitivity coefficient of
HCO M () H CO M.
4. Conclusions
A comprehensive study was conducted on the effect of methanol addition into the isooctane on laminar flame speed. Experimental study was performed in a constant volume chamber using the
spherically propagating flame at pressure of 0.1 MPa, temperatures
of 363 K and 393 K and varied methanol blending ratios. A modified model (IM model) was developed and validated with present
experimental data. Reaction pathway and sensitivity analyses were
made to clarify the change of laminar flame speed with methanol
addition into the isooctane. The main conclusions are as follows:
(1) Laminar flame speeds of isooctane flame reach the peak
around equivalence ratio of 1.1, while the peak is presented
around 1.2 for the methanol flame. With the methanol addition into isooctane, the equivalence ratio corresponding to
the peak value shifts to the rich mixture side. When methanol blending ratio is less than 40%, laminar flame speeds give
moderate increase at all equivalence ratios. Further increasing methanol blending ratio will significantly increase the
laminar flame speeds at rich mixture side while slightly
change at lean mixture side.
(2) There exists a critical equivalence ratio with the value
between 1.2 and 1.3. With the methanol addition into isooctane, Markstein length increases at the equivalence ratios
larger than the critical value; while Markstein length
decreases at the equivalence ratios smaller than the critical
value. This result of Markstein length is consistent with
the observation on the schlieren images.
(3) A modified model (IM model) was developed on the basis of
the isooctane model proposed by Chaos et al. [1]. IM model
can well predict the laminar flame speeds under all conditions.
(4) Reaction pathway analysis reveals that considerable stable
species are produced in the isooctane flame and reducing
the overall reactivity. Methanol mainly produces HCO and
generates H radical, contributing high laminar flame speed.
With the addition of methanol into the isooctane, HCO production is greatly promoted and the productions of the
stable species are inhibited. This is consistent to the sensitivity analysis and the concentrations of species. In addition,
the variation of H radical concentration provides supports
for the equivalence ratio shift of the laminar flame speed.

Acknowledgements
This work is supported by the National Natural Science Foundation of China (Grant Nos. 51406159, 91441203 and 50876085), the

National Basic Research Program (2013CB228406), the China Postdoctoral Science Foundation (2015T81025), and the State Key Laboratory of Engines, Tianjin University (K2016-02).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2016.07.087.
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