Combustion and Flame 136 (2004) 548556

www.elsevier.com/locate/jnlabr/cnf

The chemical structures of opposed flow diffusion flames

of C3 oxygenated hydrocarbons (isopropanol, dimethoxy
methane, and dimethyl carbonate) and their mixtures
A. Sinha and M.J. Thomson
Department of Mechanical and Industrial Engineering, University of Toronto, 5 Kings College Road, Toronto, ON,
M5S-3G8, Canada
Received 6 June 2003; received in revised form 12 November 2003; accepted 20 December 2003

Abstract
Species concentrations and temperatures were measured across opposed flow diffusion flames of three C3
oxygenated hydrocarbons: isopropyl alcohol, dimethoxy methane (DMM), and dimethyl carbonate (DMC). In
addition, measurements were made with propane for comparison. Measurements were repeated for mixtures of
propane and oxygenated hydrocarbons to investigate synergistic effects. The experiments were conducted at at-
mospheric pressure by withdrawing samples from the flame using a quartz microprobe coupled to an online gas
chromatograph (GC). Gas analysis was also performed using HPLC techniques. Profiles were made of tempera-
ture and of more than 16 species, including oxygenated and aromatic hydrocarbons. The isopropyl alcohol results
suggest that the presence of the OH group favors the formation of propylene, as well as acetaldehyde and ace-
tone, relative to the propane case. For DMM and DMC, the lack of CC bonds greatly reduces the formation of
ethylene, acetylene, and propylene. For example, relative to the propane flame, the ethylene levels of isopropanol,
DMM, and DMC flames were reduced by 41, 77, and 93%, respectively. In the case of DMM, significant quantities
of formaldehyde and methyl formate were measured. All intermediate hydrocarbon levels were lower for DMC
relative to DMM. The principal intermediate of DMC was formaldehyde. Mixtures of propane and oxygenates
generally had lower hydrocarbon levels than would be expected based on only additive effects. The information
provided should be of considerable utility in providing better insight into oxygenated hydrocarbon combustion, as
well as in developing and validating chemical kinetic mechanisms.
2004 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Keywords: Isopropyl alcohol; Dimethoxy methane; Dimethyl carbonate; Reaction mechanisms; Non-premixed laminar flames;
Oxidizers; Additives

1. Introduction reduces smoke emissions [13]. In particular, addi-

Oxygenated additives have been shown to reduce
soot emissions in diesel engines. Engine studies de-
termined that blending diesel fuel with oxygenates,
including alcohols, carbonates, ethers, and acetates,
* Corresponding author.
E-mail address: thomson@mie.utoronto.ca
(M.J. Thomson).
tion of dimethyl carbonate (DMC) and dimethoxy
methane (DMM) to conventional diesel fuels has re-
duced smoke emissions [1,3,4]. Results of diesel en-
gine studies suggest that addition of ethers is more
effective at reducing smoke emissions than addition
of alcohols [5], while dimethyl carbonate is more
effective than a number of ethers [1]. In diesel en-
gines, complexities due to many simultaneous para-
meters such as fluid flow, vaporization, and chemical
processes limit our ability to determine how these ad-

0010-2180/$ see front matter 2004 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.combustflame.2003.12.011
 A. Sinha, M.J. Thomson / Combustion and Flame 136 (2004) 548556
ditives operate. In contrast, opposed flow diffusion
flames provide a well-defined system that is better
suited for obtaining fundamental information.
Isopropyl alcohol (CH3 CH(OH)CH3 ), dimethoxy
methane (CH3 OCH2 OCH3 ), and dimethyl carbon-
ate (CH3 OC(=O)OCH3 ) were studied to compare
oxygenated hydrocarbons with different structures.
These compounds are, respectively, alcohols (OH),
ethers (O), and carbonyls (C(=O)). Among C3
oxygenated hydrocarbons, detailed chemical kinetic
mechanisms have been developed for methyl ac-
etate [6] and DMM [7]. These mechanisms were
validated with data from jet stirred reactors. No
mechanisms are known to exist for isopropyl alco-
hol or DMC. Recent modeling studies have noted
the need to obtain more experimental data under
well-characterized conditions [8]. This article aims
to provide better insight into oxygenated hydrocar-
bon combustion, as well as data for chemical kinetic
model validation.
2. Experimental methodology
Experiments were conducted at atmospheric pres-
sure using an opposed flow diffusion flame burner.
The burner consisted of two opposing identical stain-
less-steel outlets that direct the fuel stream and oxi-
dizer stream into a stagnation point flow. Each inlet
port consists of two co-axial cylinders 25 and 39 mm
in diameter, respectively, forming an inner tube for
the main flow (fuel or oxidizer), and an annulus for
the nitrogen co-flow. The two cylinders were mounted
co-axially, spaced 20 mm apart. To produce a uni-
form laminar flow with flat velocity profiles at the
inlet, water-cooled porous plugs were used. Both fuel
and oxidizer streams have the same inlet velocity of
10 cm/s. Fig. 1 is a schematic of the experimental
setup.
Seven different flames were studied; the condi-
tions are listed in Table 1. The oxidizer stream con-
taining O2 and N2 was sent through the top burner
Table 1
Experimental conditions
Flame
Oxidizer side
N2 O2
1. Propane 61 39
2. Isopropyl alcohol (IPA) 61 39
3. IPA and propane 61 39
4. Dimethoxy methane 61 39
5. DMM and propane 61 39
6. Dimethyl carbonate 61 39
7. DMC and propane 61 39
549
Fig. 1. Schematic of experimental setup.
port; a fuel mixture containing fuel and N2 was sent
through the bottom. The total volumetric fuel flow
rate was kept constant to ensure similar flame sizes
and shapes. The fuels included propane, isopropyl al-
cohol (IPA), DMM, and DMC, and had purities bet-
ter than 99.9%. Mixtures of propane and oxygenated
hydrocarbons were also tested. The composition and
flow rate of the oxidizer and fuel stream were chosen
in such a manner that (1) approximately equal mo-
mentum is achieved at the fuel and the oxidizer port
exits, and (2) at flame plane, the N2 /O2 ratio is near
that for air. The oxygenated hydrocarbons are pumped
using a peristaltic pump and passed through a loop
kept in a hot water bath, where they were vaporized
and mixed with the nitrogen before being routed to
the burner. In cases when only IPA, DMM, or DMC
was used as the fuel, the fuel flow lines were heated
to avoid any condensation, and the temperature of the
cooling water was raised to 45 C to avoid any con-
densation in the burner port.
Sampling was accomplished by continuously with-
drawing gases from within the flame using a quartz
microprobe with an outer diameter at the tip of 200
220 m and an orifice diameter of 120150 m;
low visible disturbance to the flame was observed.
The probe was kept stationary and the burner was
moved to measure the axial concentration profile of
Mole fraction (%)
Fuel side
Oxygenates C3 H8 N2
0 10 90
8 0 92
4 5 91
8 0 92
4 5 91
8 0 92
4 5 91
550 A. Sinha, M.J. Thomson / Combustion and Flame 136 (2004) 548556

the flame. An oil-free dual-stage heated-head vacuum

pump drew the sample from the microprobe along
heated Teflon tubing, through a filter and pushed the
sample through the sample loop of a Varian 3800 Se-
ries gas chromatograph with flame ionization detec-
tor (GC/FID). The vacuum pump (KNF Neuberger)
is made of stainless steel with a Teflon diaphragm.
A vacuum pressure of 710730 mm Hg, measured
just downstream of the microprobe, promoted rapid
cooling in the probe tip. Simultaneous reduction of
pressure and destruction of free radicals on the probe
walls were sufficient to stop the reactions and en-
sured accurate data on flame composition [9]. The
appropriate internal diameter of the microprobes was
determined by measuring the CO and CO2 levels
Fig. 2. Temperature and mole fractions of CO, CO2 , and
in the flame. As the internal diameter was progres-
C3 H8 in the propane flame. , temperature corrected for ra-
sively reduced from 340 to 170 m, the CO and CO2 diation losses; +, uncorrected for radiation losses.
concentrations increased. Below 170 m, no further
change was measured.
All runs were conducted under low- or no-soot
conditions to avoid clogging of the microprobe.
The GC system measured C1C6 species using an
HP-AL/S (50 m long, 0.53-mm i.d., and 15-m film
thickness) PLOT Column. A DB-Wax capillary col-
umn (30 m long, 0.53-mm i.d., and 1-m film thick-
ness) was used to analyze the oxygenated species in
the flame. Measurement of formaldehyde was per-
formed using HPLC technique. The carbonyls were
trapped by passing the gas samples through cartridges
containing 2,4-dinitrophenyl hydrazine (LpDNPH,
Supelco). The volume of gas that passes through the
cartridge is determined using a soap bubble flowme-
ter. Samples were then elutriated using acetonitrile,
and the liquid sample was analyzed with HPLC using Fig. 3. Mole fractions of CH4 , C2 H2 , C2 H4 , C2 H6 , p-C3 H4 ,
a variable-wavelength UV detector. CO/CO2 concen- and C3 H6 in the propane flame.
trations were measured using a separate NDIR ana-
lyzer. Temperature measurements were taken using a propane is (1) H abstraction at the primary carbon,
250-m-diameter uncoated R-type thermocouple. forming the n-propyl radical, or (2) H abstraction at
the secondary carbon, forming the isopropyl radical,
or (3) unimolecular decomposition at a CC bond,
3. Results and discussion producing ethyl and methyl radicals:

3.1. Propane C3 H8 + H = n-C3 H7 + H2 , (1)

The propane results provide a point of comparison C3 H8 + H = i-C3 H7 + H2 , (2)

for our C3 oxygenated hydrocarbon data. The flame C3 H8 + M = C2 H5 + CH3 + M. (3)
is located slightly on the oxidizer side. The thickness
of the flame is approximately 12 mm. The mea- The first pathway proceeds via scission at a CC
sured species concentrations and temperature profiles bond and forms methyl radical and ethylene. How-
(both uncorrected and corrected for radiation loss) are ever, an H radical and propylene are formed from the
shown in Figs. 2 and 3. The peak mole fraction values i-propyl radical via scission at a CH bond. The
for the major and minor species and the peak temper- ethyl radical produced during the third pathway read-
atures, uncorrected and corrected for radiation losses, ily produces ethylene,
are listed in Table 2.
n-C3 H7 + M = C2 H4 + CH3 (+M), (4)
The oxidation of propane is well known [10].
In diffusion flames, the main reaction pathway of i-C3 H7 + M = C3 H6 + H(+M), (5)
 A. Sinha, M.J. Thomson / Combustion and Flame 136 (2004) 548556 551

Table 2
Maximum measured concentrations and temperatures
Single fuel Mixtures with propane
Propane IPA DMM DMC IPA DMM DMC
TC (K)a 2036 1797 1745 1626 1871 1871 1804
TM (K) 1790 1615 1575 1485 1670 1670 1620
Peak concentrations (mole fraction)
CO 0.042 0.035 0.034 0.034 0.037 0.039 0.026
CO2 0.088 0.083 0.083 0.087 0.082 0.086 0.084
C2 H2 0.0074 0.0044 0.0017 0.00050 0.0039 0.0034 0.0022
C2 H4 0.0072 0.0028 0.0012 0.00046 0.0041 0.0038 0.0033
CH4 0.0035 0.0034 0.0030 0.0011 0.0028 0.0027 0.0019
C2 H6 0.0013 0.0011 0.0015 0.00067 0.0010 0.0012 0.00097
p-C3 H4 0.00050 0.00060 Traceb Trace 0.00055 0.00018 0.00015
C3 H6 0.0017 0.0024 Trace Trace 0.0017 0.00078 0.00075
C6 H6 80 ppm 30 ppm Trace Trace 35 ppm Trace Trace
CH3 CHO 0.0012 20 ppm
CH3 COCH3 0.0013
CH2 O Trace 0.0023 0.0016
CH3 OCHO 0.0018
a T , corrected for radiation losses; T , the measured peak temperature.
C M
b Trace means < 10 ppm.

C2 H5 + M = C2 H4 + H(+M). (6)

The formation of ethylene is favored over that of

propylene. Although the secondary hydrogen has a
lower bond energy than the primary hydrogen, at
the high flame temperatures, abstraction of the six
primary hydrogens is favored due to statistical ef-
fects. Further H abstraction from ethylene produces
in acetylene. Consequently, as is evident from Fig. 3,
the acetylene level peaks as the ethylene level starts to
decrease in the flame, and the acetylene peak occurs
later than that of ethylene. This is supported by our
measurements detecting high levels of CH4 , C2 H4 ,
and C2 H2 forming as the propane reacts. Methyl
recombination forms C2 H6 , which was detected at
Fig. 4. Temperature and mole fractions of CO, CO2 , and IPA
moderate concentrations. As expected, propylene was in the isopropyl alcohol flame. , temperature corrected for
detected in relatively lower levels compared with eth- radiation losses; +, uncorrected for radiation losses.
ylene. Propyne (p-C3 H4 ) is formed from propylene
via the allyl radical and allene. propane flame, acetaldehyde (CH3 CHO) and ace-
tone (CH3 COCH3 ) are also detected in significant
3.2. Isopropyl alcohol amounts. Formaldehyde is present at very low lev-
els.
The structural similarity of IPA to propane pro- The literature on IPA combustion chemistry is lim-
vides an interesting opportunity to investigate the ef- ited; it includes studies using flow reactors [11], diffu-
fect of the OH group in the hydrocarbon chain. Fig. 4 sion flames [12], and fundamental calculations [13].
presents species concentration profiles for the fuel These studies have reported similar compounds as
(C3 H7 OH), major products (CO, CO2 ), and the tem- products.
perature profile in the flame. The intermediate hydro- In IPA flames, the IPA reacts via H abstraction
carbon species concentrations are shown in Figs. 5 (1) at the primary carbon site, (2) at the OH group,
and 6. Peak mole fraction values for the major and or (3) at the secondary carbon. The first reaction is
minor species and peak temperatures, uncorrected
CH3 CH(OH)CH3 + X = CH3 CH(OH)CH2 + XH.
and corrected for radiation losses, are listed in Ta-
ble 2. In addition to all the species detected in the (7)
552 A. Sinha, M.J. Thomson / Combustion and Flame 136 (2004) 548556
Fig. 5. Mole fractions of CH4 , C2 H2 , C2 H4 , and C3 H6 in
the isopropyl alcohol flame.
Fig. 6. Mole fractions of CH3 CHO, CH3 COCH3 , C2 H6 , and
p-C3 H4 in the isopropyl alcohol flame.
The CH3 CH(OH)CH2 radical then can react in two
ways. It can undergo a scission reaction either at
the CO site to produce propylene and OH radical or
at the CC bond to produce vinyl alcohol and release
one methyl radical:
CH3 CH(OH)CH2 = C3 H6 + OH, (8)
CH3 CH(OH)CH2 = CH2 CHOH + CH3 . (9)
The vinyl alcohol can undergo ketoenol rearrange-
ment to form acetaldehyde (CH3 CHO). The vinyl al-
cohol can also undergo H abstraction at the oxygen
to form the vinyl-oxy radical (CH2 CHO) and then
ketene.
H abstraction at the OH group of isopropyl alcohol
is followed by scission to form acetaldehyde:
CH3 CH(OH)CH3 + X = CH3 CHOCH3 + XH, (10)
CH3 CHOCH3 = CH3 CHO + CH3 . (11)
H abstraction at the secondary carbon produces the
CH3 C(OH)CH3 radical. This radical then undergoes
a -scission reaction at the OH bond to produce ace-
tone:
CH3 CH(OH)CH3 + X = CH3 C(OH)CH3 + XH,
(12)
CH3 C(OH)CH3 = CH3 C(=O)CH3 + H. (13)
The measurements support this discussion on path-
ways. Formation of propylene via H abstraction at the
primary carbon site is favored as demonstrated by the
40% increase in peak propylene levels relative to the
propane case. Unlike propane, where the acetylene is
produced mainly from ethylene, for isopropyl alcohol
it comes mainly from the allyl and vinyl radicals via
propylene. The peak concentration profile of C2 H2 is
more than 50% higher than that of C2 H4 although
for the propane flame, the two species have similar
levels. It is observed that propyne (p-C3 H4 ) closely
tracks the propylene levels in the flame. Hence, both
propyne and propylene levels in the IPA flame are
higher relative to the propane flame.
Both acetaldehyde and acetone are measured in
significant quantities. Acetaldehyde usually under-
goes H abstraction at either CH site and is eventually
converted to CO. Acetone, on other hand, reacts to
produce one methyl radical and CH2 CO. The reaction
proceeds via H abstraction and successive scission:
CH3 COCH3 + X = CH2 COCH3 + XH, (14)
CH2 COCH3 = CH3 + CH2 CO. (15)
3.3. Propane and isopropyl alcohol mixture
A flame burning a mixture of propane and iso-
propyl alcohol is used to investigate the potential for
synergistic effects. The peak mole fraction values for
the major and minor species and the peak tempera-
tures, uncorrected and corrected for radiation losses,
are listed in Table 2. The measured species concentra-
tions are generally lower than what would be expected
from additive effects of the pure cases. In particu-
lar, the profile of C2 H2 is approximately 30% lower
than the value calculated assuming additive effects.
This suggests that the addition of isopropyl alcohol to
propane has modest synergistic effects.
3.4. Dimethoxy methane
Dimethoxy methane provides the opportunity to
investigate an oxygenated hydrocarbon that has no
CC bonds. Fig. 7 presents the species concentration
profiles for fuel (DMM), major products (CO, CO2 ),
and temperature profile in the flame. The more impor-
tant intermediate hydrocarbon species concentrations
 A. Sinha, M.J. Thomson / Combustion and Flame 136 (2004) 548556
Fig. 7. Temperature and mole fractions of CO, CO2 , and
DMM in the dimethoxy methane flame. , temperature
corrected for radiation losses; +, uncorrected for radiation
losses.
Fig. 8. Mole fractions of CH4 , CH2 O, and CH3 OCHO in the
dimethoxy methane flame.
are shown in Figs. 8 and 9. The peak mole fraction
values for the major and minor species and the peak
temperatures, uncorrected and corrected for radiation
losses, are listed in Table 2. Formaldehyde, methyl
formate, and acetaldehyde appear as important inter-
mediates in the flame.
Oxidation of DMM has been previously studied
in a jet stirred reactor at 5 bar and 8001200 K [7].
Other than all the compounds detected in our study,
methanol was also detected in noticeable amounts.
No methanol was detected in our experiments. Daly et
al. [7] attributed the formation of methanol to the fol-
lowing surface-catalyzed, low-activation-energy de-
composition of DMM:
CH3 OCH2 OCH3 = CH3 OH + CH3 CHO. (16)
Sanchez et al. [14] also reported that no trace of
methanol was found among the products.
553
Fig. 9. Mole fractions of C2 H2 , C2 H4 , and C2 H6 in the
dimethoxy methane flame.
By the use of previous studies of DMM [7,1416],
important reaction pathways can be suggested. In
diffusion flames, DMM reacts primarily via the
H-abstraction reaction at the primary carbon or the
central carbon. The former reaction produces CH3 -
OCH2 OCH2 , which rapidly dissociates via scis-
sion to produce formaldehyde (CH2 O) and methoxy
methyl radical:
CH3 OCH2 OCH3 + X = CH3 OCH2 OCH2 + XH,
(17)
CH3 OCH2 OCH2 = CH3 OCH2 + CH2 O. (18)
The H abstraction at the central carbon produces the
CH3 OCHOCH3 radical. scission produces methyl
formate (CH3 OCHO) with release of one methyl rad-
ical:
CH3 OCH2 OCH3 + X = CH3 OCHOCH3 + XH,
(19)
CH3 OCHOCH3 = CH3 OCHO + CH3 . (20)
The methoxy methyl radicals formed in Reaction
(18) will undergo further scission to form formalde-
hyde and methyl radical. Methyl formate, formed via
Reaction (20), is a stable species and is expected to
react in flame via H abstraction and successive scis-
sion as
CH3 OCHO + X = CH3 OCO + XH, (21)
CH3 OCO = CH3 + CO2 , (22)
or
CH3 OCHO + X = CH2 OCOH + XH, (23)
CH2 OCOH = CH2 O + HCO. (24)
The CH3 OCO radicals may also undergo dissociation
at the CH3 O bond to produce CH3 O radical and CO.
554 A. Sinha, M.J. Thomson / Combustion and Flame 136 (2004) 548556

Unimolecular decomposition reactions can also

be important. Unimolecular decomposition at the
CH3 O bond produces CH3 and OCH2 OCH3 radi-
cal:

CH3 OCH2 OCH3 = CH3 + OCH2 OCH3 . (25)

Further scission of OCH2 OCH3 at the CH2 O
bond produces formaldehyde and methoxy radical, or
OCH2 OCH3 may undergo decomposition at the CH
bond to produce CH3 OCHO and H radical. An al-
ternative route for the unimolecular decomposition is
cleavage of the CH3 OCH2 bond:

CH3 OCH2 OCH3 = CH3 O + CH2 OCH3 . (26)

Further reactions of the products of Reactions (25)
and (26) produce CH3 , CH2 O, and CH3 O. The
methoxy radicals are consumed primarily by fast -
scission reactions to produce formaldehyde [10,17].
Fig. 10. Temperature and mole fractions of CO, CO2 , and
DMC in the dimethyl carbonate flame. , temperature cor-
rected for radiation losses; +, uncorrected for radiation
losses.

3.5. Propane and dimethoxy methane mixture

A mixture of propane and DMM was burned in the

flame. Peak mole fraction values for the major and mi-
nor species and peak temperatures, uncorrected and
corrected for radiation losses, are listed in Table 2.
The measured species concentrations are generally
lower than what would be expected from additive ef-
fects of the pure cases. In particular, the profiles of
C2 H2 are 20% lower than the value calculated as-
suming additive effects. This suggests that addition
of DMM to propane has modest synergistic effects.

3.6. Dimethyl carbonate

Dimethyl carbonate provides the opportunity to
investigate another oxygenated hydrocarbon that has
no CC bonds. The more important species concen-
trations and temperature profiles are shown in Figs. 10
and 11. Peak mole fraction values for the major and
minor species and peak temperatures, uncorrected and
corrected for radiation losses, are listed in Table 2.
Formaldehyde is an important intermediate species
detected in the DMC flame.
It appears that DMC undergoes some decomposi-
tion during its vaporization. By looking at the mole
fractions of CO and CH2 O at the inlet, the extent of
decomposition can be estimated to be around 4%. The
concentration of fuel at the inlet port also gives a sim-
ilar value for the extent of decomposition.
Very little information on the pyrolysis or oxida-
tion chemistry of DMC is available in the literature.
Bilde et al. [18] investigated the atmospheric chem-
istry of DMC using flash photolysis and pulse radioly-
sis techniques over the temperature range 252370 K.
They outlined hydrogen removal and unimolecular
Fig. 11. Mole fractions of CH4 , C2 H2 , C2 H4 , C2 H6 , and
CH2 O in the dimethyl carbonate flame.
decomposition of DMC as the key reactions in gen-
erating a radical pool in the atmosphere.
With the DMM and dimethyl ether (DME) [17] re-
action pathways as a guide, important DMC reactions
can be suggested. H abstraction from DMC leads to
the formation of formaldehyde and CH3 OCO:
CH3 OC(=O)OCH3 + X
= CH2 OC(=O)OCH3 + XH, (27)
CH2 OC(=O)OCH3 = CH2 O + CH3 OCO. (28)
Unimolecular decomposition of DMC at the OCO
bond forms a methoxy radical and CH3 OCO:
CH3 OC(=O)OCH3 = CH3 OCO + OCH3 . (29)
However, breaking the OCH3 bond of DMC releases
a methyl radical and OC(=O)OCH3 :
CH3 OC(=O)OCH3 = CH3 OC(=O)O + CH3 . (30)
 A. Sinha, M.J. Thomson / Combustion and Flame 136 (2004) 548556
Fig. 12. A comparison of the peak mole fractions of CH4 ,
C2 H2 , C2 H4 , C3 H6 , and C6 H6 for the propane, IPA, DMM,
and DMC flames.
The CH3 OCO produced during pathways (28) and
(29) can break down through two competing reac-
tions:
CH3 OCO = CH3 + CO2 , (31)
CH3 OCO = OCH3 + CO. (32)
The CH3 OC(=O)O radicals produced in Reaction
(30) decompose via scission at the CH3 OCO bond
to produce CO2 and a methoxy radical. Thus, most
of the DMC is consumed forming methoxy radicals,
which then react to form formaldehyde.
3.7. Propane and dimethyl carbonate mixture
A mixture of propane and DMC was burned in the
flame. Peak mole fraction values for the major and mi-
nor species and peak temperatures, uncorrected and
corrected for radiation losses, are listed in Table 2.
The measured species concentrations are generally
lower than what would be expected from additive ef-
fects of the pure cases. In particular, the profiles of
C2 H2 are 40% lower than the value calculated as-
suming additive effects. This suggests that addition
of DMC to propane has synergistic effects.
3.8. Comparison
The peak mole fractions for the four flames with
a single fuel are compared in Fig. 12. Similar levels
of methane are seen for the propane, IPA, and DMM
flames. These flames form a methyl radical in all their
most important reaction pathways. The greater forma-
tion of methoxy in the DMC flame greatly reduces
its methane levels. The peak levels of C2 H2 , C2 H4 ,
and C3 H6 are much lower in the DMM and DMC
flames due to their lack of CC bonds. The C2 H2
and C2 H4 present in these flames are due to methyl
radicals combining to form ethane, which reacts to
produce ethylene and acetylene. The DMC flames
555
lower C2 H2 and C2 H4 levels relative to DMM are
consistent with the lower methane levels. The C6 H6
levels follow the trends observed in the unsaturated
hydrocarbons, as expected. Presence of the OH group
in IPA favors the formation of propylene relative to
the propane flame as discussed above.
4. Conclusions
The oxidation of propane and three different C3
oxygenates has been investigated experimentally us-
ing an opposed diffusion flame. The fuels, in order
of decreasing peak ethylene and acetylene concen-
trations, are propane, isopropanol, DMM, and DMC.
Peak benzene levels followed trends similar to those
of acetylene and ethylene. Propane, isopropanol, and
DMM had similar peak methane levels, whereas
DMC has much lower levels. Peak ethane levels were
similar to those of methane. Peak propylene lev-
els were highest for isopropanol, lower for propane,
and not detectable for DMM and DMC. Mixtures of
propane and oxygenates generally had moderately
lower measured peak hydrocarbon levels than one
would expect based on only additive effects. This syn-
ergistic effect was most significant in the case of the
acetylene levels for the propane and DMC mixtures.
Reactions are proposed to interpret the data. In the
case of propane, the major route is the formation of
n-propyl radical, which produces ethyl and methyl
radicals via scission. However, the presence of an
OH group in the case of isopropyl alcohol favors the
formation of propylene and we observe that acetylene
is formed by a pathway different from that for the
propane case. For DMM and DMC, the lack of CC
bonds greatly reduces the formation of ethylene and
acetylene. In the case of DMM, the reactions proceed
mainly via H abstraction and successive scission to
produce methyl radical and formaldehyde. The pres-
ence of oxygen on the central carbon in DMC favors
breakage of the OCO bond, forming methoxy rad-
ical, which ultimately results in very low levels of
methane, ethane, ethylene, and acetylene.
Acknowledgments
This work was supported by the Natural Science
and Engineering Research Council of Canada and the
Auto21 National Centre of Excellence.
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