The Isomerization of Dinitrogen Tetroxide:  O2N−NO2 → ONO−NO2

Pimentel, André Silva; Lima, Francisco das Chagas Alves; Silva, Albérico Borges Ferreira da

doi:10.1021/jp067805z

Cited by 58 publications

(91 citation statements)

References 74 publications

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“…Formation of NO ϩ NO 3 Ϫ is thought to be from autoionization of asymmetric N 2 O 4 (ONONO 2 ), possibly formed by sequential uptake and reaction of NO 2 on the surface (15). Recent theoretical studies (16) show that once ONONO 2 is formed, it is converted within femtoseconds to NO ϩ NO 3 Ϫ ; based on experimental studies of NO 2 on ice films, conversion of NO ϩ NO 3 Ϫ to HONO via reaction [3] is also fast (17,18).…”

mentioning

confidence: 99%

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Raff

Njegic

Chang

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

113

182

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Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NO y ) are also globally distributed, because NO formed in combustion processes is oxidized to NO 2 , HNO 3 , N 2 O 5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NO y onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO 2 or N 2 O 5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO 2 ), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO 2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist.

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mentioning

confidence: 99%

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Raff

Njegic

Chang

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

113

182

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“…[12][13][14][15][16][17][18] While the symmetric form of the dimer is favoured, there are pathways that can generate the asymmetric trans-ONONO 2 form that is the most likely precursor to the ion pair and subsequently HONO. 12,13,15,16,18 de Jesus Medeiros and Pimentel, in a study of the dimerization of NO 2 and the symmetric to asymmetric isomerization of the dimer in water clusters, predicted direct HONO formation from the NO 2 Á(H 2 O) n + NO 2 reaction and from the transition state for symmetric to asymmetric isomerization. 15 These modifications of the proposed mechanism described above bypass formation of (NO + )(NO 3 À ) through autoionization or, in the case of the NO 2 Á(H 2 O) n + NO 2 reaction, formation of the NO 2 dimer.…”

mentioning

confidence: 99%

Reaction of a charge-separated ONONO2 species with water in the formation of HONO: an MP2 Molecular Dynamics study

Varner

Finlayson-Pitts

Gerber

2014

Phys. Chem. Chem. Phys.

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À) with water is modelled in ONONO 2 Á (H 2 O) 4 clusters. Molecular Dynamics simulations using second-order Møller-Plesset perturbation (MP2) theory support the feasibility of the reaction of a charge-separated species to produce HONO and nitric acid.It is well known that nitrous acid (HONO) plays a major role in the chemistry of the atmosphere, e.g. as a source of hydroxyl (OH) radicals. 1,2 While heterogeneous reactions of NO 2 with water on tropospheric surfaces are believed to be important in generating HONO, the actual mechanisms involved are not known with certainty. On a chemical basis, the involvement of the NO 2 dimer seems reasonable, 3 although other mechanisms have been proposed for production of HONO both in the dark and under irradiation. [4][5][6][7][8][9][10][11] Initial steps of one proposed mechanism 3 include NO 2 dimerization to form N 2 O 4 and autoionization of asymmetric N 2 O 4 , i.e. ONONO 2 , to form (NO + )(NO 3 À ).ONONO 2 -(NO + )(NO 3 À )Reaction of the (NO + )(NO 3 À ) ion pair with water to form HONO and nitric acid (HONO 2 ) is the final step. A number of studies have addressed the formation of NO 2 dimers in both the symmetric (with a central NN bond) and asymmetric (ONONO 2 ) forms, and the interconversion between the two. [12][13][14][15][16][17][18] While the symmetric form of the dimer is favoured, there are pathways that can generate the asymmetric trans-ONONO 2 form that is the most likely precursor to the ion pair and subsequently HONO. 12,13,15,16,18 de Jesus Medeiros and Pimentel, in a study of the dimerization of NO 2 and the symmetric to asymmetric isomerization of the dimer in water clusters, predicted direct HONO formation from the NO 2 Á(H 2 O) n + NO 2 reaction and from the transition state for symmetric to asymmetric isomerization. 15 These modifications of the proposed mechanism described above bypass formation of (NO + )(NO 3 À ) through autoionization or, in the case of the NO 2 Á(H 2 O) n + NO 2 reaction, formation of the NO 2 dimer. Further exploration of the (NO + )(NO 3 À ) path will allow for comparison between potential routes and provide additional insight into the detailed mechanism that converts NO 2 in the presence of water to HONO. This is particularly useful for understanding other important reactions of NO 2 on surfaces in the presence of water, such as the reaction with HCl to form ClNO, since such chemistry likely shares common intermediates with NO 2 hydrolysis. [19][20][21] In ab initio Molecular Dynamics [AIMD], the reaction trajectory is propagated classically on the ab initio potential surface providing a means for studying reactive processes and the influence of the immediate environment. 22 The system wave function or electron density is calculated at each time step, i.e. on-the-fly, for determination of the energy, the interatomic forces and other properties. Partial charges are an obvious metric to investigate charge separation in the reaction of an ion pair as charge characteristics can indicate a shift in the nature of the interactio...

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“…Reactions R7 and R8 represent the further oxidation of glyoxylic acid (HOC-COOH) to oxalic acid (HOOC-COOH), through the same paths as R5-R6, involving the formation of a nitrite intermediate and ONONO 2 which is the isomer of dinitrogen tetroxide (N 2 O 4 ). ONONO 2 will decompose to NO 2 through the equilibrium reactions R9 and R10 [79]. Reaction R11 is the decomposition of oxalic acid, which was reported [80,81] to form formic acid HCOOH and CO 2 which were observed in the experiments.…”

Section: Decomposition Of Tmeda·8hnomentioning

confidence: 69%

Spray and Combustion of Gelled Hypergolic Propellants for Future Rocket and Missile Engines

Thynell¹,

Adair²,

Goddard³

et al. 2014

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The Isomerization of Dinitrogen Tetroxide: O₂N−NO₂ → ONO−NO₂

Cited by 58 publications

References 74 publications

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Reaction of a charge-separated ONONO2 species with water in the formation of HONO: an MP2 Molecular Dynamics study

Spray and Combustion of Gelled Hypergolic Propellants for Future Rocket and Missile Engines

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