Ab initio study of protonated nitrosamide: a possible intermediate in the deNO x process

Kulkarni, Sudhir A.; Pundlik, Savita S.

doi:10.1016/0009-2614(95)00999-k

Cited by 13 publications

(12 citation statements)

References 15 publications

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“…The key step for the ionic DeNO x process in flames has been recently suggested to involve the generation of the NH 3 NO + ion. , However, NH 3 NO + has not been observed in flames. The absence of the NH 3 NO + ion has been suggested to be due to fast proton-transfer reactions between NH 3 NO + and NH 3 or H 2 O species to form H 2 NNO and NH 4 + or H 3 O + , respectively.…”

Section: Discussionmentioning

confidence: 99%

“…Recently, a possible alternative ionic process involving the formation of a protonated nitrosamide (H 3 NNO + ) has been suggested. , In this process, the fast proton-transfer reaction of the H 3 NNO + ion produces nitrosamide (H 2 NNO) as an intermediate species. Subsequent dissociation of H 2 NNO occurs through two main reaction pathways 1-3 Therefore, the study of the chemical reactions of the mixed cluster ions of NO and NH 3 molecules should be helpful in understanding the chemical mechanisms occurring in this process.…”

Section: Introductionmentioning

confidence: 99%

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Observation of Magic Numbers within NO/NH₃ Mixed Cluster Ions

1998

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The metastable decomposition of photoionized NO/NH 3 clusters has been investigated employing a reflectron time-of-flight mass spectrometer. The metastable dissociation spectra of the most prominent cluster ion species NO + (NH 3 ) n (3 e n e 28) show that the rate coefficient for the loss of one NH 3 molecule from the cluster rapidly increases up to n ) 13 and thereafter is nearly independent of the cluster size. This is interpreted as evidence of a stable structure that consists of a central NO + ion surrounded by a first solvation shell of 12 NH 3 molecules.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Observation of Magic Numbers within NO/NH₃ Mixed Cluster Ions

1998

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“…Such molecularly adsorbed NH 3 , if in the vicinity of surface nitrite (LM11), will naturally form LM12, which eventually evolves into NH 3 NO + (LM13). We would like to point out that earlier experimental 60 and theoretical work 60,61 concluded that NH 3 NO + is apt to lose a proton when it interacts with a proton acceptor such as H 2 O or NH 3 . Our calculations show that LM14 can undergo a proton transfer (TS11) to give the NH 2 NO species (LM2) with a barrier of 2.1 kcal mol À1 .…”

Section: Nitrite Mechanismmentioning

confidence: 93%

Brønsted-NH4+ mechanism versusnitrite mechanism: new insight into the selective catalyticreduction of NO by NH3

Yuan

et al. 2011

Phys. Chem. Chem. Phys.

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The selective catalytic reduction (SCR) of NO by NH(3) over V(2)O(5)-based catalysts is used worldwide to control NO(x) emission. Understanding the mechanisms involved is vital for the rational design of more effective catalysts. Here, we have performed a systematic density functional theory (DFT) study of a SCR reaction by using cluster models. Three possible mechanisms have been considered, namely (i) a Lewis acid mechanism, (ii) a Brønsted acid mechanism and (iii) a nitrite mechanism. Our calculations down-play the significance of mechanism (i) due to its high barrier as well as the incorrect reaction order. On the other hand, our calculations demonstrate that both mechanisms (ii) and (iii) can lead to a first order reaction with respect to NO with the predicted barriers being consistent with the experimental observations. Thus, we conclude: there exists two competitive pathways for SCR. Mechanism (ii) is dominant when the Brønsted acidity of the catalysts is relatively strong, while mechanism (iii) becomes important when Brønsted acidity is weak or absent. Importantly, we demonstrate that the latter two mechanisms share a common feature where N-N bond formation is ahead of N-H bond cleavage, in contrast to that in mechanism (i). Such a sequence provides an effective way to reduce the side reaction of ammonia combustion since the relatively strong N-N bond has already been formed.

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“…It was demonstrated that the N-protonated species, NH 3 ϩ -NO, is the most stable isomer [13,18,19,22] and that the eclipsed conformer 1a , see Figure 1, is a true minimum while the staggered cation represents a rotational transition state [18]. In the present study, all this information is obviously confirmed, but in addition, we obtained very accurate thermochemical data, such as NOA (NH 3 Table 3 and since all the PA and IE values are in really good agreement with the reference data, we can be quite confident in our NOA (ammonia) calculated value of 125.7 kJ mol Ϫ1 .…”

Section: Nitrosonium Complexes Of Ammonia and Methylaminementioning

confidence: 99%

Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study

Gerbaux

Wantier

Flammang

2004

J. Am. Soc. Mass Spectrom.

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Recent studies have demonstrated the biological importance of the interaction of nitric oxide with proteins such as cytochrome-c or hemoglobin. In particular, the possibility that the nitrosonium cation, NO ϩ , could reversibly bind to sulfide atom type was proposed. At pH values of biological relevance, nitrosation was proposed to occur through the action of NO ϩ carriers such as nitrosothiols or nitrosamines. In this context, the gas phase chemistry of protonated nitrosothiols is studied in the present work by a combination of mass spectrometry and computational methods. (J Am Soc Mass Spectrom 2004, 15, 344 -355)

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Ab initio study of protonated nitrosamide: a possible intermediate in the deNO x process

Cited by 13 publications

References 15 publications

Observation of Magic Numbers within NO/NH₃ Mixed Cluster Ions

Observation of Magic Numbers within NO/NH₃ Mixed Cluster Ions

Brønsted-NH4+ mechanism versusnitrite mechanism: new insight into the selective catalyticreduction of NO by NH3

Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study

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Ab initio study of protonated nitrosamide: a possible intermediate in the deNO x process

Cited by 13 publications

References 15 publications

Observation of Magic Numbers within NO/NH3 Mixed Cluster Ions

Observation of Magic Numbers within NO/NH3 Mixed Cluster Ions

Brønsted-NH4+ mechanism versusnitrite mechanism: new insight into the selective catalyticreduction of NO by NH3

Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study

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Observation of Magic Numbers within NO/NH₃ Mixed Cluster Ions

Observation of Magic Numbers within NO/NH₃ Mixed Cluster Ions