School of Aerospace Engineering

Chemical Kinetics:
NOx Mechanisms
Jerry Seitzman

0.2 2500

2000
0.15

Temperature (K)
Mole Fraction

CH4 1500
0.1 H2O
HCO x 1000 1000
Temperature
0.05
500
Methane Flame
0 0
0 0.1 0.2 0.3
Distance (cm)

KineticsNOx -1

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
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School of Aerospace Engineering

Overview
• Having now examined mechanisms for fuel
oxidation (H2, CO and HC), the goal here is to revisit
mechanisms for NOx production:
1. thermal mechanism (extended Zeldovich) for high T,
lean conditions
2. N2O mechanism for low T, lean conditions
3. NNH mechanism for high T, stoich/rich, H2
4. Fenimore/prompt mechanism for hydrocarbon fuel-
conversion zones
5. NO2 mechanism for NONO2 conversion in low T
regions
KineticsNOx -2

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
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NOx Formation
• NOx (NO, NO2, NO3) important pollutant
– NO2 leads to acid rain/photochemical smog/O3
– combustion NO converted to NO2 in atmosphere
– can also directly impact human health
• Observation: original Zeldovich mechanism does
not accurately predict NO production in
– wet air
– low T combustion with long residence times
– stoichiometric and rich H2-air flames
– low residence time or rich hydrocarbon flames
• Need more advanced NO mechanisms
KineticsNOx -3

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
All rights reserved.

School of Aerospace Engineering

Thermal NO Mechanism
• Already described basic Zeldovich mechanism
– add reaction for “wet” systems (H species) HR
Extended N2  O  NO  N { NO.1} +75.1 kcal/mol
Zeldovich O2  N  NO  O {NO.2}  32.1 kcal/mol
Mechanism
OH  N  NO  H {NO.3} 48.7 kcal/mol
• Thermal NO Formation
– still rate limited by { NO.1f }
– dominates at high T (>~1800K), lean environments
– long res usually required (postflame gases)
– superequilibrium [O], [OH] increases NO prod. rate
KineticsNOx -4

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
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Intermediate N2O Mechanism

• N2 first converted to N2O then NO HR
N2  O M   N2O M  { NO.4} 40 kcal/mol
N 2O  H  NO  NH {NO.5} +35 kcal/mol
N 2O  O  NO  NO {NO.6} 36 kcal/mol
compete with N 2O  H  N 2  OH NO.7
N2O destruction via N 2O  O  N 2  O2 NO.8
• NO Formation N 2O  OH  N 2  HO2 NO.9
– {NO.4} has Lindemann-like p dependence (k0k)
– medium to high activation energies
• Ea(kcal/mol)~18{NO.4}; 35{NO.5}; 23{NO.6}
– important in low T, fuel lean ( <~ 0.8) systems (+ high p)
– NH from {NO.5} can also lead to NO
NH  O  NO  H NO.10 NH  O2  NO  OH NO.11
KineticsNOx -5

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
All rights reserved.

School of Aerospace Engineering

NNH Mechanism
• Thermal + nitrous mechanisms “ok” for H2-air, BUT
• NO also produced via NNH intermediate HR
N 2  H  M   NNH  M  { NO.12 } +6.5 kcal/mol
NNH  O  NO  NH {NO.13} 11.3 kcal/mol
• {NO.13} has same products as{NO.5}
– and NH can also lead to NO via {NO.10 and .11}
• Where is NNH mechanism (path) important?
– for T >~ 2200 K, important for stoichiometric and rich,
low residence time systems, H2-air flames
– for T >~ 1900 K, most impact (relative to thermal NOx)
near stoichiometric (and at lower T)
KineticsNOx -6

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
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Fenimore/Prompt Mechanism
• In thermal, N2O, and NNH mechanisms, NO produced
via conversion from attack on N2/O2 via radicals
containing only N, O, H nuclei
• Sufficient for wet air and hydrogen combustion
• NO can also be produced in hydrocarbon combustion
via C species
– prompt NOx – Fenimore observed NO formed earlier in
HC combustion than possible from thermal mechanism
• General reaction scheme
– CHx (e.g., CH, CH2 and CH3) radicals react with
molecular nitrogen to form HCN (hydrogen cyanide)
– conversion to NO through various intermediates
KineticsNOx -7

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
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School of Aerospace Engineering

Fenimore Scheme
• Early version of the mechanism
• Rate limiting step
CH  N2  HCN  N conversion of N2
• Conversion to NO
HCN  O  NCO  H
NCO  H  NH  CO
NH  H  N  H2
N  OH  NO  H
– conversion to NO via radical/radical reactions
• Limited accuracy (e.g., <1.2)
KineticsNOx -8

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
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General Prompt Mechanism

• Many reactions for range of rich mixtures/fuels
– graphical representation (ref. Bowman, 24th
Combustion Symposium) C

H, OH O NO
CN N
CHx N2 H2,H2O O2, OH
H, OH N2
O H
HCN NCO NH OH,O2

Fuel-N O H2 H, OH NO
OH also in
HNCO NH2 thermal mech.
H
NH3
CHx (x=1,2,3)
KineticsNOx -9

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
All rights reserved.

School of Aerospace Engineering

NO2 Mechanism
• Noted that NO converted to NO2 in atmosphere
– combustion systems also convert NO to NO2
• can sometimes be significant fraction of total
combustor NOx emissions [NO]+[NO2]
NO  HO2  NO2  OH {NO2 .1} HO2 formed @ low T

NO2  H  NO  OH {NO2 .2} forward reactions

(NO2 recycled to
NO2  O  NO  O2 {NO2 .3} NO) active at high T
• No NO2 from hot regions
• NO2 in combustion systems often comes from NO
formed in hotter regions mixing into low T regions
KineticsNOx -10

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
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Example: Premixed Laminar Flame

• NO2, prompt important in reaction zone; thermal in downstream
Cold Post-flame region
Flame
NO Production Rate (mole/cm3/s)

0.40 reactants Total

0.30 =0.85
NH+HN+H2
 Prompt mech.
0.20
N+O2 Primary source of N?
N+OH
0.10 NO2+H N2+O  Thermal Mech.

0
2 ms 3 ms 4 ms
CH4/air position in flame converted to Time
-0.10
1 atm
300K/80F inlet HO2+NONO2+OH
KineticsNOx -11

Copyright © 2004-2005, 2012, 2016, 2020-2021 by Jerry M. Seitzman.

AE/ME 6766 Combustion
All rights reserved.