The Role of Nitric Oxide in Photochemistry

Heicklen, Julian; Cohen, N.

doi:10.1002/9780470133354.ch3

Cited by 84 publications

(9 citation statements)

References 359 publications

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“…However, some authors 2,3,6–9,12,13 use a two‐step mechanism to describe their experimental results when they are derived from Equation (2). A literature review from Heicklen and Cohen 26 summarizes most of these studies, and the two main mechanisms are a first mechanism (M‐I) with a dimer of NO as an intermediate:

N {normalO}_{((), g)} + E ⇆_{k_{- 2}}^{k_{2}} {((), NO)}_{2 (normalg)}

{((), NO)}_{2 (normalg)} + {normalO}_{2 (normalg)} \overset{k_{3}}{\to} 2 N {normalO}_{2 (normalg)}

r_{normalNO} = \frac{k_{2} * k_{3} * {([], NO)}^{2} * [O_{2}]}{k_{- 2} + k_{3} * [O_{2}]}

and a second mechanism (M‐II) with NO 3 as an intermediate:

N {normalO}_{((), g)} + {normalO}_{2 (normalg)} ⇆_{k_{- 4}}^{k_{4}} N {normalO}_{3 (normalg)}

N {normalO}_{3 (normalg)} + N {normalO}_{((), g)} \overset{k}{\to}

…”

Section: Literature Reviewmentioning

confidence: 99%

“…The two two‐step mechanisms (M‐I) and (M‐II) have been compared by Baulch et al 25 , Heincklen and Cohen, 26 Hisatsune and Zafonte, 14 and Olbregts 19 . All of them have reached the conclusion that the two mechanisms are possible interpretations for the nitric oxide oxidation.…”

Section: Literature Reviewmentioning

confidence: 99%

“…They also suggest the mechanism (M-II) to describe the oxidation of nitric oxide rather than the mechanism (M-I) because NO 3 has been identified spectroscopically. 28 The two two-step mechanisms (M-I) and (M-II) have been compared by Baulch et al 25 , Heincklen and Cohen, 26 Hisatsune and Zafonte, 14 and Olbregts. 19 All of them have reached the conclusion that the two mechanisms are possible interpretations for the nitric oxide oxidation.…”

Section: Literature Reviewmentioning

confidence: 99%

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Kinetic study of the nitric oxide oxidation between 288 and 323 K, under pressure, focus on the oxygen influence on the reaction rate constant

Neyrolles

Cruz

Bassil

et al. 2020

Int J of Chemical Kinetics

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The sequestration of carbon dioxide fumes from oxyfuel combustion is used to reduce significantly the carbon dioxide emissions from coal‐fired power plants. Impurities like nitric oxide, present in the fumes, can cause technical difficulties during the capture, the treatment, the transport, and the storage steps of the CO2 fumes. The purpose of this study is to better understand the oxidation of nitric oxide under pressure in the presence of carbon dioxide and in the experimental condition of flue gas treatment. This reaction is known to be a third‐order reaction, two order in nitric oxide and first order in oxygen. To examine the effect of the temperature, the pressure and the volume fraction of oxygen on the rate constant of oxidation, k1, an autoclave is used. The first experiment studies the influence of the temperature between 288 and 323 K. The results found are in the form of an Arrhenius‐type equation: k1 = 810 exp(620/T) and are in agreement with the literature. Carbon dioxide does not seem to have an influence on the rate constant, whereas our experimental measurements indicate an influence of the volume fraction of oxygen. The rate constant decreases when the oxygen volume fraction increases by up to 10%. Then the rate constant remains constant. This observation allows us to conclude that the mechanism involving the mechanism with a dimer of NO as an intermediate is more likely to be the mechanism involved in the nitric oxide oxidation in our experimental conditions: high pressure and ambient temperature. The rate constant k2, k–2, and k3 were also estimated in these conditions.

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N {normalO}_{((), g)} + E ⇆_{k_{- 2}}^{k_{2}} {((), NO)}_{2 (normalg)}

{((), NO)}_{2 (normalg)} + {normalO}_{2 (normalg)} \overset{k_{3}}{\to} 2 N {normalO}_{2 (normalg)}

r_{normalNO} = \frac{k_{2} * k_{3} * {([], NO)}^{2} * [O_{2}]}{k_{- 2} + k_{3} * [O_{2}]}

and a second mechanism (M‐II) with NO 3 as an intermediate:

N {normalO}_{((), g)} + {normalO}_{2 (normalg)} ⇆_{k_{- 4}}^{k_{4}} N {normalO}_{3 (normalg)}

N {normalO}_{3 (normalg)} + N {normalO}_{((), g)} \overset{k}{\to}

…”

Section: Literature Reviewmentioning

confidence: 99%

Section: Literature Reviewmentioning

confidence: 99%

Section: Literature Reviewmentioning

confidence: 99%

See 1 more Smart Citation

Kinetic study of the nitric oxide oxidation between 288 and 323 K, under pressure, focus on the oxygen influence on the reaction rate constant

Neyrolles

Cruz

Bassil

et al. 2020

Int J of Chemical Kinetics

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“…109 Oxygen, chlorine, bromine, and (in part) hydrogen (Equations 4.10-4.13) all follow the rate law shown in Equation 4.14. 112 -114 Heicklen found evidence for the operation of both mechanisms, 111 with perhaps the best argument for the common operation of the dimer mechanism being Occam's razor, as only one common mechanism is consistent with all of the data. In addition to being unusual third order gas phase reactions, they also have a negative temperature coefficient, so the reaction slows at higher temperatures.…”

Section: The Kinetics Of Nitric Oxide's Termolecular Reactionsmentioning

confidence: 91%

The Nitrogen Oxides: Persistent Radicals and van der Waals Complex Dimers

Bohle¹

2010

Stable Radicals

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“…Formation of NO 3 radicals in the reaction [9][10][11] NO + O 2 + M => ON-O-O(•) + M (6) can enhance the contribution of chain mechanism due to reactions…”

Section: The Possible Role Of No 3 Radicalsmentioning

confidence: 99%

The Chain Reaction of Atmospheric Nitrogen Oxidation, Initiated by an Electric Discharge in Air

Vg¹

2015

J Phys Chem Biophys

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The data, concerning to the nitrogen oxidation reaction, initiated by electrical discharge, are reviewed in this article. The reviewed data lead to conclusion that critical concentrations of NO molecules and NO 3 radicals can be achieved in course of discharge in air at some special conditions, thereafter avalanche-like rise of reaction velocity is observed. At explosion conditions the oxidation of nitrogen proceeds until full exhaustion of atmospheric oxygen in the reaction zone. Explosion like kinetics of nitrogen oxidation results in high concentration of electronically excited molecules NO(B 2 Π), it forms conditions for laser generation in the blue region of the spectrum. The generation of this kind was observed. The proposed mechanism of chain reaction explains all the experimental data.

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The Role of Nitric Oxide in Photochemistry

Cited by 84 publications

References 359 publications

Kinetic study of the nitric oxide oxidation between 288 and 323 K, under pressure, focus on the oxygen influence on the reaction rate constant

Kinetic study of the nitric oxide oxidation between 288 and 323 K, under pressure, focus on the oxygen influence on the reaction rate constant

The Nitrogen Oxides: Persistent Radicals and van der Waals Complex Dimers

The Chain Reaction of Atmospheric Nitrogen Oxidation, Initiated by an Electric Discharge in Air

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