Investigation into the pressure dependence between 1 and 10 Torr of the reactions of NO2 with CH3 and CH3O

Biggs, Peter J.; Canosa‐Mas, Carlos E.; Fracheboud, Jean-Marc; Parr, Adam; Shallcross, Dudley E.; Wayne, Richard P.; Caralp, F.

doi:10.1039/ft9938904163

Cited by 57 publications

(73 citation statements)

References 23 publications

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“…1.4 · 10 mol s , room temperature measurements by Yamada et al [11] and Biggs et al [12], which is also in good agreement with the determination by Glänzer and Troe of cm 3 [10] at How-13 Ϫ1 Ϫ1…”

Section: ϫ1 ϫ1supporting

confidence: 85%

“…For this reason, the addition reaction (R2) has either been neglected or included with a very low rate constant in most previous studies of nitromethane decomposition. QRRK calculations [12] indicate that at room temperature channel (R14), forming CH 3 O and NO, accounts for a fraction 0.975 of the energized CH 3 ONO at zero pressure, and that this fraction drops only to 0.723 by 10 atm.…”

Section: Reaction Setmentioning

confidence: 99%

“…1.4 · 10 mol s perature [11,12]. Very little work has been reported on the addition step forming methyl nitrite (R2).…”

Section: Introductionmentioning

confidence: 99%

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Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Glarborg¹,

Bendtsen²,

Miller³

1999

Int. J. Chem. Kinet.

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The thermal decomposition of nitromethane under highly diluted conditions in shock tubes has been analyzed in terms of a detailed chemical kinetic model. The experimental data were adopted from Glä nzer and Troe, Hsu and Lin, and Zhang and Bauer, respectively; they cover the temperature range and pressures from 0.5 to 6.0 bar. Based on 1000-1400 K these results, rate constants for the reactions (R1) andThe high and low pressure limits for reaction (R1) determined by Glä nzer and Troe have been shown to be consistent with more recent shock tube data, provided a center broadening parameter is introduced to describe the fall-off behavior. Our reinterpretation of the shock tube results of Glä nzer and Troe together with room temperature measurements indicate that the rate constant for (R14) decreases slightly with temperature, as cm mol s . order of magnitude faster than recombination of CH 3 and NO 2 to form nitromethane. Based on the available data for the forward and reverse rate of reaction (R1) a value of 66.7 Ϯ 2.0 cal/(mol K) for the entropy S 0,298 of CH 3 NO 2 is estimated.

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Section: ϫ1 ϫ1supporting

confidence: 85%

Section: Reaction Setmentioning

confidence: 99%

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Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Glarborg¹,

Bendtsen²,

Miller³

1999

Int. J. Chem. Kinet.

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“…The agreement between the studies of , Biggs et al (1993), and Martínez et al (2000) appears satisfactory, in particular if the different ways of treating the falloff curve are taken into account. We assume similar values of k 01 for M=Ar and N 2 .…”

Section: Comments On Preferred Valuessupporting

confidence: 70%

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

et al. 2006

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Abstract. This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.

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“…As methoxy (CH 3 O) radicals can be generated by techniques such as pulsed laser photolysis and microwave discharge and detected with high sensitivity by LIF (Shannon et al, 2013;Chai et al, 2014;Albaladejo et al, 2002;Biggs et al, 1993Biggs et al, , 1997, the method has been used in kinetic studies of a range of CH 3 O reactions. These studies used the electronic excitation of the methoxy radical from the ground state to the first electronically excited state (A 2 A 1 ← X 2 E).…”

Section: Introductionmentioning

confidence: 99%

A new method for atmospheric detection of the CH<sub>3</sub>O<sub>2</sub> radical

et al. 2017

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Abstract.A new method for measurement of the methyl peroxy (CH 3 O 2 ) radical has been developed using the conversion of CH 3 O 2 into CH 3 O by excess NO with subsequent detection of CH 3 O by fluorescence assay by gas expansion (FAGE) with laser excitation at ca. 298 nm. The method can also directly detect CH 3 O, when no nitric oxide is added. Laboratory calibrations were performed to characterise the FAGE instrument sensitivity using the conventional radical source employed in OH calibration with conversion of a known concentration of OH into CH 3 O 2 via reaction with CH 4 in the presence of O 2 . Detection limits of 3.8 × 10 8 and 3.0 × 10 8 molecule cm −3 were determined for CH 3 O 2 and CH 3 O respectively for a signal-to-noise ratio of 2 and 5 min averaging time. Averaging over 1 h reduces the detection limit for CH 3 O 2 to 1.1 × 10 8 molecule cm −3 , which is comparable to atmospheric concentrations. The kinetics of the second-order decay of CH 3 O 2 via its self-reaction were observed in HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry) at 295 K and 1 bar and used as an alternative method of calibration to obtain a calibration constant with overlapping error limits at the 1σ level with the result of the conventional method of calibration. The overall uncertainties of the two methods of calibrations are similar -15 % for the kinetic method and 17 % for the conventional method -and are discussed in detail. The capability to quantitatively measure CH 3 O in chamber experiments is demonstrated via observation in HIRAC of CH 3 O formed as a product of the CH 3 O 2 self-reaction.

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Investigation into the pressure dependence between 1 and 10 Torr of the reactions of NO2 with CH3 and CH3O

Cited by 57 publications

References 23 publications

Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

A new method for atmospheric detection of the CH<sub>3</sub>O<sub>2</sub> radical

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Investigation into the pressure dependence between 1 and 10 Torr of the reactions of NO2 with CH3 and CH3O

Cited by 57 publications

References 23 publications

Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

A new method for atmospheric detection of the CH&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; radical

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A new method for atmospheric detection of the CH<sub>3</sub>O<sub>2</sub> radical