Spectroscopy of the thermal oxidation of NO in solid oxygen at cryogenic temperatures

Smith, George R.; Guillory, William A.

doi:10.1016/0022-2852(77)90438-6

Cited by 36 publications

(52 citation statements)

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“…Traces B and C are difference spectra using A as background to remove the interference pattern (present in trace A < 300 cm À1 ). [28] that have previously been reported at 642, 488, and 304 cm À1 agree well with those observed herein. This species is most likely formed from (NO) 2 dimer and O 2 that were both trapped in the same matrix cage.…”

Section: Uv and Far Ir Spectra Of No/o 2 Reaction Productssupporting

confidence: 94%

Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO₃ Radical

2009

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By codeposition of NO/Ne and O(2)/Ne mixtures at 6 K, weakly bound complexes between O(2) and NO are formed. They exhibit a strong, structured charge transfer UV band at lambda(max)=275 nm. The UV band disappears during UV irradiation of the neon matrix, while the visible spectrum of the NO(3) radical appears. Simultaneously, the fundamental nu(4) of the NO(3) radical in the X (2)A(2)' ground state is observed in infrared absorption for the first time at 365.6 cm(-1). Its (14/15)N and (16/18)O isotopic shifts reveal strong couplings between the two e'-type modes of NO(3), which are both active in a pseudo-Jahn-Teller interaction with the excited B (2)E' electronic state. The dispute on the vibrational fundamentals of the NO(3) radical is now concluded by the unambiguous assignment of combination bands associated with the fundamental nu(4). Taking into account the observed isotopic shifts and estimated anharmonicities for nu(4) and the most intense IR band of NO(3) at 1492 cm(-1) (nu(3)+nu(4)), the frequency of the so far not observed fundamental nu(3) is estimated to be 1100+/-10 cm(-1). A tentative assignment of the vibronic levels in the IR spectrum in the range from 1000 to 3000 cm(-1) is given.

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Section: Uv and Far Ir Spectra Of No/o 2 Reaction Productssupporting

confidence: 94%

Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO₃ Radical

2009

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“…McKee [4] subsequently carried out a quantum-chemical study using B3LYP/6-31G(d) and MP2/6-31G(d) calculations. The major result of these studies led to the conclusion that the key intermediate in the oxidation of NO is an isomeric structure of dinitrogen tetroxide, namely, iso-N 2 O 4 [11] or a peroxide, trans-trans O=NO-ON=O [4].…”

Section: Experimental Data and Formulation Of The Problemmentioning

confidence: 98%

“…We should note that the study of Smith and Guillory [11] was overlooked by many workers (see references in the work of Gadzhiev et al [1]). However, we find important data in this work, which we want to analyze and explain on the basis of our model for reaction (1).…”

Section: Experimental Data and Formulation Of The Problemmentioning

confidence: 99%

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DFT calculations of the intermediate and transition state in the oxidation of NO by oxygen in the gas phase

Захаров

Minaev

2011

Theor Exp Chem

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The B3LYP density functional method using the extended basis set 6-311++G(3df) was used to calculate the stationary points along the reaction coordinate 2NO + O 2 ® 2NO 2 . The results of the calculation were compared with the reported physicochemical characteristics of this reaction. The origin of the barrierless activation of the oxygen molecule and driving force for the spontaneous oxidation of NO were examined.In 1774, the English chemist, Joseph Priestly, carried out the reaction 3Cu + 8HNO 3 ® 3Cu(NO 3 ) 2 + 2NO + 4H 2 O and called the gaseous product, NO, "nitrous air." He also noted that "nitrous air" had the property of acquiring a brown color upon mixing with air. Thus, Priestly was the first to discover the oxidation of nitric oxide to give nitrogen dioxideThe molecular mechanism of this reaction remained a mystery for 230 years throughout the entire history of modern chemistry until Gadzhiev et al. [1] have recently come close to its complete explanation.Nitric oxide (NO) is an intermediate in the industrial production of nitric acid. This process involves two major steps: 1) the oxidation of ammonia to give nitric oxide (NO) and 2) the conversion of NO into nitric acid through the oxidation of NO to NO 2 . Trimolecular reaction (1) has second-order kinetics relative to NO and first-order kinetics relative to oxygen [2]. This reaction is one of the few reported cases, in which, up to 600 K, the rate not only does not increase but actually decreases [3], giving rise to a negative observed activation energy, which has been a topic for discussion for many years [1][2][3][4][5][6][7][8].The major scheme for the mechanism proposed for the anomalous temperature dependence of the rate of reaction (1) has rested on the assumption that only (NO) 2 dimers, the probability of formation of which decreases with increasing temperature, take part in the reaction [2, 3]:(2a) 2NO « (NO) 2 , 0040-5760/11/4702-0093

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“…The absorptions due to the N-18-N species appeared to be much weaker than those of the N-16-N isotopomers located at 635.3 [20,21].…”

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confidence: 82%

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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Spectroscopy of the thermal oxidation of NO in solid oxygen at cryogenic temperatures

Cited by 36 publications

References 23 publications

Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO₃ Radical

Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO₃ Radical

DFT calculations of the intermediate and transition state in the oxidation of NO by oxygen in the gas phase

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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Spectroscopy of the thermal oxidation of NO in solid oxygen at cryogenic temperatures

Cited by 36 publications

References 23 publications

Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO3 Radical

Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO3 Radical

DFT calculations of the intermediate and transition state in the oxidation of NO by oxygen in the gas phase

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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Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO₃ Radical

Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO₃ Radical

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