The Nuclear Industry

Congedo, Tom; Lahoda, Edward J.; Matzie, R.A.; Task, Keith

doi:10.1007/978-0-387-27843-8_21

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“…[1] During these experiments we noticed the formation of various N 2 O 4 species by either thermal or photochemical reactions. Because such binary nitrogen oxides are of considerable significance in tropospheric air pollution, [2] physiological systems, [3,4] and industrial processes, [5] we decided to explore in more detail the formation of these N 2 O 4 species by photochemical isomerisation of sym-N 2 O 4 (D 2h ) and from NO and molecular O 2 isolated in solid Ne.…”

Section: Introductionmentioning

confidence: 99%

Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N₂O₂⋅O₂ complex and of sym‐N₂O₄ in Solid Ne Matrices

Beckers

Zeng

Willner

2010

Chemistry A European J

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Pure sym-N(2)O(4) isolated in solid Ne was obtained by passing cold neon gas over solid N(2)O(4) at -115 degrees C and quenching the resulting gaseous mixture at 6.3 K. Filtered UV irradiation (260-400 nm) converts sym-N(2)O(4) into trans-ONONO(2), a weakly interacting (NO(2))(2) radical pair, and traces of the cis-N(2)O(2)O(2) complex. Besides the weakly bound ONO(2) complex, cis-N(2)O(2)O(2) was also obtained by co-deposition of NO and O(2) in solid Ne at 6.3 K, and both complexes were characterised by their matrix IR spectra. Concomitantly formed cis-N(2)O(2) dissociated on exposure to filtered IR irradiation (400-8000 cm(-1)), and the cis-N(2)O(2)O(2) complex rearranged to sym-N(2)O(4) and trans-ONONO(2). Experiments using (18)O(2) in place of (16)O(2) revealed a non-concerted conversion of cis-N(2)O(2)O(2) into these species, and gave access to four selectively di-(18)O-substituted trans-ONONO(2) isotopomers. No isotopic scrambling occurred. The IR spectra of sym-N(2)O(4) and of trans-ONONO(2) in solid Ne were recorded. IR fundamentals of trans-ONONO(2) were assigned based on experimental (16/18)O isotopic shifts and guided by DFT calculations. Previously reported contradictory measurements on cis- and trans-ONONO(2) are discussed. Dinitroso peroxide, ONOONO, a proposed intermediate in the IR photoinduced rearrangement of cis-N(2)O(2)O(2) to the various N(2)O(4) species, was not detected. Its absence in the photolysis products indicates a low barrier (

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Section: Introductionmentioning

confidence: 99%

Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N₂O₂⋅O₂ complex and of sym‐N₂O₄ in Solid Ne Matrices

Beckers

Zeng

Willner

2010

Chemistry A European J

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The Nuclear Industry

Cited by 1 publication

References 6 publications

Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N₂O₂⋅O₂ complex and of sym‐N₂O₄ in Solid Ne Matrices

Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N₂O₂⋅O₂ complex and of sym‐N₂O₄ in Solid Ne Matrices

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The Nuclear Industry

Cited by 1 publication

References 6 publications

Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N2O2⋅O2 complex and of sym‐N2O4 in Solid Ne Matrices

Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N2O2⋅O2 complex and of sym‐N2O4 in Solid Ne Matrices

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Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N₂O₂⋅O₂ complex and of sym‐N₂O₄ in Solid Ne Matrices

Intermediates Involved in the Oxidation of Nitrogen Monoxide: Photochemistry of the cis‐N₂O₂⋅O₂ complex and of sym‐N₂O₄ in Solid Ne Matrices