Mechanism of the CH3NH2–HNO2 reaction: Ab initio DFT/TST study

Tiwary, Amit S.; Mukherjee, Asok K.

doi:10.1016/j.theochem.2009.05.020

Cited by 8 publications

(2 citation statements)

References 41 publications

(52 reference statements)

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“…Its fate, however, is not entirely clear. HONO is known to undergo homogeneous self-reaction, with a computed activation energy of 56 kJ mol –1 , to generate N 2 O 3 which can reenter the catalytic cycle.…”

Section: Resultsmentioning

confidence: 99%

Experimental and Computational Interrogation of Fast SCR Mechanism and Active Sites on H-Form SSZ-13

Zheng

Gao

et al. 2017

ACS Catal.

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Experiments and density functional theory (DFT) models are combined to develop a unified, quantitative model of the mechanism and kinetics of fast selective catalytic reduction (SCR) of NO/NO2 mixtures over H-SSZ-13 zeolite. Rates, rate orders, and apparent activation energies collected under differential conditions reveal two distinct kinetic regimes. First-principles thermodynamics simulations are used to determine the relative coverages of free Brønsted sites, chemisorbed NH4 +, and physisorbed NH3 as a function of reaction conditions. First-principles metadynamics calculations show that all three sites can contribute to the rate-limiting N–N bond forming step in fast SCR. The results are used to parametrize a kinetic model that encompasses the full range of reaction conditions and recovers observed rate orders and apparent activation energies. Observed kinetic regimes are related to changes in most-abundant surface intermediates.

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Section: Resultsmentioning

confidence: 99%

Experimental and Computational Interrogation of Fast SCR Mechanism and Active Sites on H-Form SSZ-13

Zheng

Gao

et al. 2017

ACS Catal.

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“…Accurate reaction kinetic data can better predict the experimental results. 42 In this work, the temperaturedependent reaction rate constants (k) of the R1−R7 channels were calculated by the TST theory. The high-pressure-limit calculation conditions were set.…”

Section: Reaction Mechanism Of Ap Decompositionmentioning

confidence: 99%

Mechanism of Interaction between Ammonium Perchlorate and Aluminum

Yan,

Xu,

Nie

et al. 2023

J. Phys. Chem. A

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There is an interactive effect between ammonium perchlorate (AP) and aluminum (Al) powder during the combustion process of composite solid propellants, but the mechanism of this effect is still lacking. Using quantum chemical methods, we investigated this mechanism from a molecular perspective. The interaction process between Al and AP was analyzed by comparing the chemical bond changes between the atoms during the reaction process of the Al/AP system and the AP unimolecular thermal decomposition system. The results show that Al atoms alter the reaction mechanism of AP thermal decomposition, significantly decreasing the activation energy of AP decomposition at high temperature but increasing that at low temperature. Meanwhile, the temperature-dependent rate constant of each basic reaction was calculated by transition state theory. The rate constants increase with temperature. Under high temperature and pressure, Al can increase the high-temperature decomposition rate of AP by up to 1–3 orders of magnitude.

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DFT studies of the adsorption and dissociation of H2O on the Al13 cluster: origins of this reactivity and the mechanism for H2 release

Zhao

Zhao²,

Gao³

et al. 2013

J Mol Model

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A theoretical study of the chemisorption and dissociation pathways of water on the Al₁₃ cluster was performed using the hybrid density functional B3LYP method with the 6-311+G(d, p) basis set. The activation energies, reaction enthalpies, and Gibbs free energy of activation for the reaction were determined. Calculations revealed that the H₂O molecule is easily adsorbed onto the Al13 surface, forming adlayers. The dissociation of the first H₂O molecule from the bimolecular H₂O structure via the Grotthuss mechanism is the most kinetically favorable among the five potential pathways for O-H bond breaking. The elimination of H₂ in the reaction of an H₂O molecule with a hydrogen atom on the Al cluster via the Eley-Rideal mechanism has a lower activation barrier than the elimination of H₂ in the reaction of two adsorbed H atoms or the reaction of OH and H. Following the adsorption and dissociation of H₂O, the structure of Al₁₃ is distorted to varying degrees.

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Mechanism of the CH3NH2–HNO2 reaction: Ab initio DFT/TST study

Cited by 8 publications

References 41 publications

Experimental and Computational Interrogation of Fast SCR Mechanism and Active Sites on H-Form SSZ-13

Experimental and Computational Interrogation of Fast SCR Mechanism and Active Sites on H-Form SSZ-13

Mechanism of Interaction between Ammonium Perchlorate and Aluminum

DFT studies of the adsorption and dissociation of H2O on the Al13 cluster: origins of this reactivity and the mechanism for H2 release

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