The pressure dependence of the thermal decomposition of N2O

Röhrig, Michael; Petersen, Eric L.; Davidson, David F.; Hanson, Ronald K.

doi:10.1002/(sici)1097-4601(1996)28:8<599::aid-kin5>3.3.co;2-t

Cited by 19 publications

(44 citation statements)

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“…12b highlights the role of the dissociation reaction of N 2 O, which is also responsible of NO x formation via the nitrous oxide mechanism in combustion systems. These experimental data were already successfully modeled by Konnov [56] who adopted the reaction rate parameters suggested by Rohrig et al [57] for the dissociation of N 2 O and were close to the values used in the mechanism of Li and Williams [58]. We use the reaction rate parameters suggested by Johnsson et al [59] and employed in the mechanisms of Bendtsen et al [60].…”

Section: H 2 /Air Mixtures In a Stirred Reactormentioning

confidence: 85%

A wide range modeling study of NOxNOx formation and nitrogen chemistry in hydrogen combustion

Frassoldati

Faravelli

Ranzi

2006

International Journal of Hydrogen Energy

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Section: H 2 /Air Mixtures In a Stirred Reactormentioning

confidence: 85%

A wide range modeling study of NOxNOx formation and nitrogen chemistry in hydrogen combustion

Frassoldati

Faravelli

Ranzi

2006

International Journal of Hydrogen Energy

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“…The conditions behind the reflected shock were calculated from the incident shock speed using pressure-dependent enthalpies provided by the Sandia thermodynamic data-base [14] and the Peng -Robinson equation of state as described in [15]. Details of these calculations using the Sandia real-gas code will be presented elsewhere [16].…”

Section: Methodsmentioning

confidence: 99%

A shock tube study of the pyrolysis of NO2

Röhrig

Petersen

Davidson

et al. 1997

Int. J. Chem. Kinet.

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NO 2 concentration profiles in shock-heated NO 2 /Ar mixtures were measured in the temperature range of 1350 -2100 K and pressures up to 380 atm using Ar ϩ laser absorption at 472.7 nm, IR emission at , and visible emission at 300 -600 nm. In the course of this study, the absorption coefficient of NO 2 at 472.7 nm was measured at temperatures from 300 K to 2100 K and pressures up to 75 atm. Rate coefficients for the reactions and were derived by comparing the measured and calculated NO 2 profiles. For reaction (1), the following low-and high-pressure limiting rate coefficients were inferred which describe the measured fall-off curves in Lindemann form within 15%:The inferred rate coefficient at the low-pressure limit, k 1o , is in good agreement with previous work at higher temperatures, but the energy of activation is lower by 20 kJ/mol than reported previously. The pressure dependence of k 1 observed in the earlier work of Troe [1] was confirmed. The rate coefficient inferred for the high pressure limit, k 1ϱ , is higher by a factor of two than Troe's value, but in agreement with data obtained by measuring specific energydependent rate coefficients.For the reactions (2a) and (2b), least-squares fits of the present data lead to the following Arrhenius expressions:For reaction (2), the new data agree with previously recommended values of k 2a and k 2b , although the present study suggests a slightly higher preexponential factor for k 2a . © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 483 -493, 1997. k 2b ϭ 10 13.0Ϯ0.3 exp(Ϫ(108 Ϯ 8) kJ mol Ϫ1 / RT) cm 3 mol Ϫ1 s Ϫ1 k 2a ϭ 10 12.3Ϯ0.2 exp(Ϫ(105 Ϯ 7) kJ mol Ϫ1 / RT) cm 3 mol Ϫ1 s Ϫ1 k 1ϱ ϭ 10 (14.6Ϯ0.3) exp(Ϫ300 kJ mol Ϫ1 / RT) s Ϫ1 k 1o ϭ 10 (15.6Ϯ0.2) exp(Ϫ(251 Ϯ 5) kJ mol Ϫ1 /RT) cm 3 mol Ϫ1 s Ϫ1 (2b) NO 2 ϩ NO 2 : NO 3 ϩ NO NO 2 ϩ M : NO ϩ O ϩ M (1), NO 2 ϩ NO 2 : 2NO ϩ O 2 (2a), 6.25 Ϯ 0.25 m

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“…The reason for the low impact of the N 2 S mechanism is that the S-atom concentration is always much lower than those of the O/H radicals. (10) is insignificant compared to reaction (8). Under stoichiometric and lean conditions, where the rates of 7 and 10 become comparable in magnitude, the concentration of atomic S is small, 3-4 orders of magnitude lower than [H] and [O], and negligible amounts of N 2 S are formed.…”

Section: Combustion Implicationsmentioning

confidence: 92%

“…The experimental high-pressure limit for N 2 O dissociation is k ∞ = 1.3 × 10 13 exp(−262 kJ mol −1 /RT) s −1 . 8 The activation energy E a is only 4 kJ mol −1 above the E 0 cited above for the MECP, and the pre-exponential factor is 2-3 orders of magnitude smaller than typical for a simple bond fission reaction. 40 This reflects the small probability for intersystem crossing.…”

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Predicted thermochemistry and unimolecular kinetics of nitrous sulfide

Marshall

Gao

Glarborg

2011

The Journal of Chemical Physics

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The geometry of N2S was obtained at the CCSD(T)/aug-cc-pV(T + d)Z level of theory and energies with coupled-cluster single double triple (CCSD(T)) and basis sets up to aug-cc-pV(6 + d)Z. After correction for anharmonic zero-point energy, core-valence correlation, correlation up to CCSDT(Q) and relativistic effects, D0 for the N–S bond is estimated as 71.9 kJ mol−1, and the corresponding thermochemistry for N2S is ${\rm \Delta }_{\rm f} {\rm H}_0^ \circ = 205.4\,{\rm kJ}\,{\rm mol}^{ - 1}$ΔfH0∘=205.4 kJ mol −1 and ${\rm \Delta }_{\rm f} {\rm H}_{298}^ \circ = 202.6\,{\rm kJ}\,{\rm mol}^{ - 1}$ΔfH298∘=202.6 kJ mol −1 with an uncertainty of ±2.5 kJ mol−1. Using CCSD(T)/aug-cc-pV(T + d) theory the minimum energy crossing point between singlet and triplet potential energy curves is found at r(N–N) ≈ 1.105 Å and r(N–S) ≈ 2.232 Å, with an energy 72 kJ mol−1 above N2 + S(3P). Application of Troe's unimolecular formalism yields the low-pressure-limiting rate constant for dissociation of N2S k0 = 7.6 × 10−10 exp(−126 kJ mol−1/RT) cm3 molecule−1 s−1 over 700–2000 K. The estimated uncertainty is a factor of 4 arising from unknown parameters for energy transfer between N2S and Ar or N2 bath gas. The thermochemistry and kinetics were included in a mechanism for CO/H2/H2S oxidation and the conclusion is that little NO is produced via subsequent chemistry of NNS.

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The pressure dependence of the thermal decomposition of N2O

Cited by 19 publications

References 0 publications

A wide range modeling study of NOxNOx formation and nitrogen chemistry in hydrogen combustion

A wide range modeling study of NOxNOx formation and nitrogen chemistry in hydrogen combustion

A shock tube study of the pyrolysis of NO2

Predicted thermochemistry and unimolecular kinetics of nitrous sulfide

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