NOx reduction by reburning: theoretical study of the branching ratio of the HCCO+NO reaction

Vereecken, Luc; Raman, Sumathy; Carl, Shaun A.; Peeters, Jozef

doi:10.1016/s0009-2614(01)00818-1

Cited by 40 publications

(58 citation statements)

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“…10,[37][38][39][40] As Figure 1 indicates, of the two dominant channels for this reaction, (5a) and (5b), a propensity to form HCN favors the propagation of the reaction series toward N 2 , whereas formation of HCNO is thought to lead to recycling of NO via fast reaction of HCNO with OH and O. 39 So far, only three experimental determinations of the rate constant of reaction 5 have been published; two of which are at room temperature only, the other is a relative rate determination.…”

Section: Introductionmentioning

confidence: 99%

Absolute Rate Coefficient of the HCCO + NO Reaction over the Range T = 297−802 K

et al. 2002

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The absolute rate coefficient of the gas-phase reaction HCCO + NO was experimentally determined for the first time over an extended temperature range, 297-802 K. HCCO radicals were generated by pulsed-laser photolysis of CH 2 CO at 193 nm. Their subsequent decay, under pseudo-first-order conditions, was monitored in real time using a newly developed laser-photofragment/laser-induced fluorescence technique (Carl, S. A.; Sun, Q.; Peeters, J. J. Chem. Phys. 2000, 114, 10332) that involved pulsed-laser photodissociation of HCCO at 266 nm and laser-induced fluorescence at ca. 430 nm of the resulting nascent rotationally excited CH(X 2 Π) photofragment. The rate coefficient of the title reaction was found to exhibit a negative temperature dependence described by k 5 (T) (HCCO+NO) ) (1.6 ( 0.2) × 10 -11 exp(340 ( 30 K/T) cm 3 s -1 molecule -1 (2σ errors). In combination with the recent theoretically determined branching ratios for this reaction of this laboratory (Vereecken, L.; Sumathy, R.; Carl, S. A.; Peeters, J. Chem. Phys. Lett. 2001, 344, 400), the temperature dependencies of the two dominant product channels, HCN + CO 2 and HCNO + CO, may be described by k 5a ) (3.7 ( 0.3) × 10 -10 T -0.72(0.02 exp(200 ( 30 K/T) cm 3 s -1 molecule -1 and k 5b ) (1.4 ( 0.2) × 10 -11 exp(320 ( 30 K/T) cm 3 s -1 molecule -1 , respectively, where the given (2σ) error limits are derived from those of the present experimental work only.

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Section: Introductionmentioning

confidence: 99%

Absolute Rate Coefficient of the HCCO + NO Reaction over the Range T = 297−802 K

et al. 2002

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“…where the H 2 molecule keeps unchanged in the subprocess 3 → P 7 . It is obvious that the pathway P 7 possesses 10 steps from R to P 7 .…”

Section: Pathway Of P 1 and Pmentioning

confidence: 99%

“…It is obvious that the pathway P 7 possesses 10 steps from R to P 7 . By comparing the pathway P 7 with the pathway P 1 , it is easy to find out the two pathways possess same steps from R to b 2 , i.e., four steps.…”

Section: Pathway Of P 1 and Pmentioning

confidence: 99%

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A density functional investigation of the reaction mechanism of H₂O + HCNO

Kong

Wang

2010

Int J of Quantum Chemistry

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A theoretical investigation of the H 2 O + HCNO reaction, which is carried out by means of CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p)+ZPVE computational method to determine a set of reasonable pathways, there are seven product pathways, P i with i = 1, 2, . . . , 7 are involved. It is shown that P 1 (H 2 O + NCOH), P 2 (CO + NH 2 + OH), P 4 (HCN + HO 2 + H), and P 6 (CO + NH 2 OH) are the major product channels; and P 7 (HOC + H 2 + NO) is the minor product channels, whereas the other channels for P 3 (HNO + HCOH) and P 5 (HNO + H 2 CO) are very minor, the minor product channels.

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“…41 We have contributed to improving our understanding of this complex NO x chemistry by investigating reactions such as C 2 HϩNO, 28,24 NOϩC 2 H 2 , 42 NOϩC 2 H 3 , 43 and HCCOϩNO. 44,45 Rate constants for the reaction C 2 HϩNO 2 represent significant missing data in NO x chemistry at combustion temperatures. We have thus focused our attention on this reaction in the present work.…”

Section: Introductionmentioning

confidence: 99%

An experimental and theoretical study of the reaction of ethynyl radicals with nitrogen dioxide (HC≡C+NO2)

Carl

Nguyen

et al. 2003

The Journal of Chemical Physics

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Pulsed laser photolysis and quantum chemical-statistical rate study of the reaction of the ethynyl radical with water vapor Potential energy surface for the CH 3 + HBr → CH 4 + Br hydrogen abstraction reaction: Thermal and stateselected rate constants, and kinetic isotope effects A pulsed laser photolysis/chemiluminescence ͑PLP/CL͒ technique was used to determine absolute rate constants of the reaction C 2 HϩNO 2 →products over the temperature range 288 -800 K at a pressure of 5 Torr (N 2 ). The reaction has a large rate constant that decreases with increasing temperature. It may be expressed in simple Arrhenius form as k 1 (T)ϭ(7.6Ϯ1.0) ϫ10 Ϫ11 exp͓(130Ϯ50) K/T͔, although there is an indication of a downward curvature for T Ͼ700 K. A three-parameter Arrhenius fit to the data, which takes this into account gives k 1 (T) ϭ(9.7Ϯ1.5)ϫ10 Ϫ9 T Ϫ0.68 exp͓(158Ϯ65) K/T͔. Our experiments also show that the 293 K rate constant is invariant to pressure between 2 and 11 Torr (N 2 ). We have also characterized the C 2 HϩNO 2 reaction theoretically. A large portion of the potential energy surface ͑PES͒ of the ͓C 2 ,H,N,O 2 ͔ system has been investigated in its electronic ͑singlet͒ ground-state using DFT with the B3LYP/6-311ϩϩG(3d f ,2p) method and MO computations at the CCSD(T)/6-311ϩ ϩG(d,p) level of theory. Seventeen isomers and thirty-two transition structures were found to connect reactants to products following eighteen different channels. Hydroxyl cyano ketone 11 and formylisocyanate 16 were found to be the most stable intermediates, although the reaction flux through them, as a fraction of the total, is likely to be small over the temperature range studied. A part of the PES corresponds with that of the HCCOϩNO reaction ͓I. V. Tokmakov, L. V. Moskaleva, D. V. Paschenko, and M. C. Lin, J. Phys. Chem. A 167, 1066 ͑2003͔͒, and the dominant product channels for C 2 HϩNO 2 proceed via the same nitrosoketene intermediate that is formed initially in the HCCOϩNO reaction. However, unlike in the latter reaction, the fate of the much more highly excited nitrosoketene formed by C 2 HϩNO 2 is likely to be governed dynamically. We present arguments as to the likely product channels for C 2 HϩNO 2 based on both statistical and dynamical considerations. A statistical description overwhelmingly favors the product set HCCOϩNO. Dynamical considerations on the other hand favor both the HCNϩCO 2 and HCCOϩNO product sets. Formation of HCNOϩCO appears unlikely. Energetically allowed paths, leading to five other product sets, namely, HNCOϩCO, HOCNϩCO, HOCCϩNO, HONCϩCO, and HNC ϩCO 2 , have also been identified, and are discussed.

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NOx reduction by reburning: theoretical study of the branching ratio of the HCCO+NO reaction

Cited by 40 publications

References 16 publications

Absolute Rate Coefficient of the HCCO + NO Reaction over the Range T = 297−802 K

Absolute Rate Coefficient of the HCCO + NO Reaction over the Range T = 297−802 K

A density functional investigation of the reaction mechanism of H₂O + HCNO

An experimental and theoretical study of the reaction of ethynyl radicals with nitrogen dioxide (HC≡C+NO2)

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NOx reduction by reburning: theoretical study of the branching ratio of the HCCO+NO reaction

Cited by 40 publications

References 16 publications

Absolute Rate Coefficient of the HCCO + NO Reaction over the Range T = 297−802 K

Absolute Rate Coefficient of the HCCO + NO Reaction over the Range T = 297−802 K

A density functional investigation of the reaction mechanism of H2O + HCNO

An experimental and theoretical study of the reaction of ethynyl radicals with nitrogen dioxide (HC≡C+NO2)

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A density functional investigation of the reaction mechanism of H₂O + HCNO