chemical kinetics of combustion processes · kinetic modeling studies of iso-butane and iso-butene...
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Chemical Kinetics of Combustion Processes
Hai WangB. Yang, J. Camacho, S. Lieb, S. Memarzadeh,
S.-K. Gao and S. Koumlis
University of Southern California
2010 CEFRC Conference
Benzene + O(3P) → Products• Overall rate coefficient extensively studied, but the products and branching
ratios not well known.
• Theoretical challenges in dealing with spin-state crossing.
Figure 1. Branching ratios observed as afunction of temperature at 4 Torr for (a)m/z=94/93 and m/z=66/65 by magnetic sectormass spectrometer (filled symbols) and time-of-flight mass spectrometer (open symbols), and (b)branching ratios determined by time-of-flightmass spectrometer. Lines are drawn to guide theeye. Error bars are 2σ-standard deviations.
• Product distributions determined over 300 to 1000 K and 1 to 10 Torr (with Taatjes/Sandia).
• Cyclopentadiene was directly identified for the first time, in addition to phenol and phenoxy.
• ab initio calculations (with Krylov/ USC) and master equation/RRKM modeling for data extrapolation.
Taatjes, C. A., Osborn, D. L., Selby, T. M., Meloni, G., Trevitt, A. J., Epifanivskii, E. Krylov, A. I., Sirjean, B., Dames, E., Wang, H. “Products of the benzene + O(3P) reaction,” Journal of Physical Chemistry A, 114, 3355-3370 (2010)
Benzene + O(3P) → ProductsR
elat
ive
Ener
gy (
kcal
/ m
ol )
20
+ O (3P)
+ CO
HO
ISC
0
–20
–40
–60
–80
–100
3A’, 1A’, 3A”, 1A”within 8 kcal/mol
1 2 3
45
6
7 8
9
10
11
+ H
O
OO
C
O
OO
O
OH
+ HCO
+H+CO
Rel
ativ
e En
ergy
( kc
al /
mol
)
20
+ O (3P)
+ CO
HO HO
ISC
0
–20
–40
–60
–80
–100
3A’, 1A’, 3A”, 1A”within 8 kcal/mol
1 2 3
45
6
7 8
9
10
11
+ H
O
OOOO
C
O
C
O
OOOO
O
OHOH
+ HCO
+H+CO
Benzene + O(3P) → Products
Table 6. Branching ratios experimentally determined and computed for reaction R1. Branching ratio
Reaction channel P (Torr) T (K) Experimental Computational C6H5OH (9) 4 700 0.58 ± 0.08a 0.56 (0.65)d 4 800 0.47 ± 0.08a 0.43 (0.50)d 4 900 0.33 ± 0.08a 0.29 (0.37)d 10 800 0.59 ± 0.08a 0.51 (0.61)d 10 900 0.41 ± 0.09a 0.40 (0.49)d C6H5O• (3) + H• 4 700 0.18 ± 0.08a 0.18 4 800 0.24 ± 0.10a 0.21 4 900 0.33 ± 0.13a 0.23 10 800 0.19 ± 0.09a 0.21 10 900 0.28 ± 0.12a 0.23 C5H6 (11) + CO 4 700 0.22 ± 0.05a 0.17 4 800 0.27 ± 0.06a 0.29 4 900 0.33 ± 0.08a 0.40 10 800 0.21 ± 0.05a 0.18 10 900 0.27 ± 0.07a 0.28
Kinetic Modeling Studies of Iso-butane and Iso-butene Combustion (work-in-progress)
• Chemical kinetic submodel of iso-butanol combustion.• In collaboration with N. Hansen/Sandia through Bin Yang (roving postdoc).• A total of 61 datasets considered, including two burner stabilized flames (30
Torr) probed by Synchrotron Photoionization Molecular Beam Mass Spectrometry (Hansen/Yang).
• Preliminary results show that USC Mech II behaves rather well against the data, but improvements are needed for the initial pyrolysis and oxidation of isobutane and isobutene.
• Chemical kinetic submodel of iso-butanol combustion.• In collaboration with N. Hansen/Sandia through Bin Yang.• A total of 61 datasets considered, including two burner stabilized flames (30
Torr) probed by Synchrotron Photoionization Molecular Beam Mass Spectrometry.
• Preliminary results show that USC Mech II behaves rather well against the data, but improvements are needed for the initial pyrolysis and oxidation of isobutane and isobutene.
Oehlschlaeger et al. (2004) Koshi and coworkers (2007)
Kinetic Modeling Studies of Iso-butane and Iso-butene Combustion (work-in-progress)
Sooting Behaviors of n- and iso-Butanol Flames (Work-in-Progress)
• Fuel-rich chemistry and sooting behaviors of butanol isomers are unknown.
• Soot formation characterized in burner-stabilized stagnation flames.
Burner-stabilized stagnation flame approach
Abid et al. (2009)
Distance, H (cm)1.2
5001.00.80.60.40.20.0
1000
1500
Tem
pera
ture
, T(K
)
1.2
Hp = 0.55 cm0.6
0.7
0.8
1.0
Distance, H (cm)1.2
5001.00.80.60.40.20.0
1000
1500
Tem
pera
ture
, T(K
)
1.2
Hp = 0.55 cm0.6
0.7
0.8
1.0
1.2
0.6
0.7
0.8
1.0
Diameter, Dp (nm)3 5 10 20 50
108
1010
dN/d
logD
p
Hp = 0.55 cm
1.2
0.6
0.7
0.8
1.0
Diameter, Dp (nm)3 5 10 20 50
108
1010
dN/d
logD
p
Hp = 0.55 cm
cooling assembly
1cmHp
stagnation plate/sample probe (Ts)
Tb
r
xu
v
to SMPScarrier N2
Sooting Behaviors of n- and iso-Butanol Flames (Work-in-Progress)
• Fuel-rich chemistry and sooting behaviors of butanol isomers are unknown.
• Soot formation characterized in burner-stabilized stagnation flames.
• No significant difference between n-butanol and isobutanol in particle inception and soot mass growth.
• Soot formed show a strong and persistent nucleation behavior well into the post flame.
• In comparison to comparable ethylene flames, soot inception in butanol flames takes substantially longer reaction time, but once nucleation starts, surface reaction is as fast as the ethylene flames.
107
108
109
1010
1011
10 100
Hp = 0.90 cm
10 100
Hp = 1.10 cm
10 100
Hp = 1.20 cm
10 100
Hp = 1.40 cm
10 100
Hp = 1.50 cm
dN/d
logD
p (cm
-3)
Diameter, Dp (nm)
PAH Precursor Chemistry (1)
PAH formation is sensitive to a multitude of elementary reactions and local flame conditions.
Accurate prediction of PAH formation may require a precision in main flame chemistry currently unavailable.
PAH formation can be highly sensitive to fuel structures.
Possibly a large number of pathways to PAHs have yet been considered.
-0.5 0.0 0.5 1.0
H+O2=O+OHHO2+H=OH+OH
HO2+OH=O2+H2OHCO+O2=CO+HO2
CH+H2=CH2+HCH2+O2=CO2+H+H
CH2*+H2=CH3+HC2H2+O=CH2+CO
C2H2+OH=C2H+H2OC2H2+H(+M)=C2H3(+M)
HCCO+H=CH2*+COHCCO+CH3=C2H4+CO
C2H3+O2=C2H3O+O
C2H2+CH2*=C3H3+HC2H2+CH2=C3H3+H
C3H3+OH=C3H2+H2OC3H3+OH=C2H3+HCO
C3H3+C3H3=>A1c-C6H4+H=A1-
C4H2+H=n-C4H3
A1+H=A1-+H2A1+OH=A1-+H2O
A1-+H(+M)=A1(+M)n-A1C2H2+C2H2=A2+H
A2+OH=A2-1+H2OA2-1+H(+M)=A2(+M)
A2C2HA*+H(+M)=A2C2HAA2C2HA+OH=A2C2HA*+H2
A2C2HA*+C2H2=A3-4P2+H=P2-+H2
P2-+C2H2=A3+HA3+H=A3-4+H2
A3-4+H(+M)=A3(+M)A3-4+C2H2=A4+H
Logarithmic Sensitivity Coefficient
Main flamechemistry
First aromaticring
Aromatic growthchemistry
Spectral sensitivity of pyrene concentration90 Torr burner stabilized C2H2/O2/Ar flame(Bockhorn), H = 0.55 cm
Wang & Frenklach, C&F (1997)
PAH Precursor Chemistry (2)Thermokinetic Origin of PAH Formation/Growth Beyond HACA
C2H2 5 5 4 4 3 2 2 1 0H 1 0 1 0 0 1 0 0 1H2 0 1 1 2 2 2 3 3 3
0.0
0.5
–0.5
–1.0∆G○
(kca
l/mol
-C)
r
+C2H2(–H)+H(–H2)
+H(–H2)
+C2H2
+C2H2(–H)
+H(–H2)
+C2H2
+C2H2(–H)
+H (+M)
+H (+M)
+H (+M) +H (+M)
••
•
•
•+H (+M)
C2H2 5 5 4 4 3 2 2 1 0H 1 0 1 0 0 1 0 0 1H2 0 1 1 2 2 2 3 3 3
0.0
0.5
–0.5
–1.0∆G○
(kca
l/mol
-C)
r
+C2H2(–H)+H(–H2)
+H(–H2)
+C2H2
+C2H2(–H)
+H(–H2)
+C2H2
+C2H2(–H)
+H (+M)
+H (+M)
+H (+M) +H (+M)
•••
••
••
••+H (+M)
• While HACA captures the thermokinetic requirements for PAH formation, its reversibility opens it to competitions from other pathways
Soot Nucleation (1)
C/H
1.2-2
~2
~10
C
B
A
C/H
1.2-2
~2
~10
C
B
A
Violi/D’Anna
Frenklach/WangMiller
Homann
Soot Nucleation (2)
10
100
10 100
coroneneB
indi
ng E
nerg
y (c
kal/m
ol)
Number of C atoms
ovalene
circumcoronene
chrysene benzo[ghi]perylenepyrene
anthracene & phenanthrene
naphthalene
10-5
10-4
10-3
10-2
10-1
100
200
400
600
800
1 2 3 4 5 6 7
Rel
ativ
e C
once
ntra
tion
Number of Aromatic Rings
Boi
ling/
Subl
imat
ion
Tem
pera
ture
(K)
10
100
10 100
coroneneB
indi
ng E
nerg
y (c
kal/m
ol)
Number of C atoms
ovalene
circumcoronene
chrysene benzo[ghi]perylenepyrene
anthracene & phenanthrene
naphthalene
10-5
10-4
10-3
10-2
10-1
100
200
400
600
800
1 2 3 4 5 6 7
Rel
ativ
e C
once
ntra
tion
Number of Aromatic Rings
Boi
ling/
Subl
imat
ion
Tem
pera
ture
(K)
Herdman and Miller (2008)
Binding energy of coronene = 25 kcal/mol
Soot Nucleation (3)
( )6
0 1
1+ 1 4
exp 1 i Bii B
H E h k Th k T
νν=
∆ ≅ − + − −
∑
( )
( )νν
σσπ
ν −=
∆ ≅
+ − − −
∑
3 2 23 01
422
6
1
2ln
ln 11
i B
i B
u B
h k Ti Bh k Ti
h pS BR m ek T
h k Te
e
Is 25.4 kcal/mol enough to bind a pair of coronene together?
2 coronene → (coronene)2
Assumptions:vi = 200 cm-1
B (cm-1) = 1510 x MW-2.12
σ2 = 1
• ∆G○ too positive to allow binding above 1000 K• Entropy tears the dimer apart.
Ovalene E0 = 35 kcal/molCircumcoronene E0 = 63 kcal/molOnly circumcoronenes bind > 1600 K.
10-8
10-6
10-4
10-2
100
0 500 1000 1500 2000 2500
T (K)
coronene
ovalene
circumcoronene
(b)
Kp
(atm
-1)
Soot Nucleation (1)
C/H
1.2-2
~2
~10
C
B
A
C/H
1.2-2
~2
~10
C
B
A
Violi/D’Anna
Frenklach/Miller
Homann
Possible, but not general
Soot Nucleation (4)• Polyacenes are singlet diradicals (though arguable).
• Ground-state polyacenes are close-shell singlets, but the adiabatic S0-T1 excitation energy is only 13 kcal/mol for heptacene - Hajgató et al. (2009).
• Applications in organic light emitting diodes and organic semiconductors and capacitors.
Soot Nucleation (5)
• Zigzag edges of graphene have localized π-electronic states
Kobayashi 1993; Klein 1994
• Zigzag edges have an open-shell singlet ground state
e.g., Fujita et al. 1996; Nakada 1996
• Finite-sized graphenes have radical or even multiradical characteristics.
e.g., Nakano et al. 2008, Nagai 2010
• Side chain can induce π-radical characteristics
Nakano et al. 2007
• Nonlinear optics applications.
i = 1 2 3 4
j = 1
2
3
i j y i j y1 1 0.000 1 3 0.0372 1 0.050 2 3 0.2173 1 0.149 3 3 0.5104 1 0.281 4 3 0.806
zigzag edge
Arm
chai
r edg
e
i = 1 2 3 4
j = 1
2
3
i j y i j y1 1 0.000 1 3 0.0372 1 0.050 2 3 0.2173 1 0.149 3 3 0.5104 1 0.281 4 3 0.806
i j y i j y1 1 0.000 1 3 0.0372 1 0.050 2 3 0.2173 1 0.149 3 3 0.5104 1 0.281 4 3 0.806
zigzag edge
Arm
chai
r edg
e
Nagai et al. 2010UBHandHLYP/6-31G(D) calculations 0 ≤ y ≤ 1y = 0: close shell singlety = 1: open shell singlet (diradical)
Soot Nucleation - Summary
• If PAHs with π-radicals do play a role in soot nucleation, we need to
•Understand the nature and structures of these PAH species,
•Determine their binding energies with relevant species, including aromatics,
•Probe them in flames (however small their concentrations may be),
•Account for the mechanism of their formation.
Work Summary
• Products of benzene + O(3P) reaction
• Kinetic modeling studies of iso-butane and iso-butene combustion
• Sooting behaviors of isobutanol and n-butanol flames
• Aromatic π-diradicals in soot nucleation and mass growth