The thermal decomposition of nitromethane under high pressure

Makovky, A.; Gruenwald, Theodor B.

doi:10.1039/tf9595500952

Cited by 21 publications

(7 citation statements)

References 3 publications

(3 reference statements)

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“…Glänzer and Troe [56,57] conducted shock tube experiments with highly diluted mixtures of CH 3 NO 2 in Ar at 900-1400 K and 1.1-41 bars to determine the rate coefficients for both the disproportionation reaction (R10) and the thermal dissociation of CH 3 NO 2 (R32). Their recommended rate coefficients in Lindemann format have found support in studies conducted at low [58,59], intermediate [60][61][62], and high temperatures [63][64][65][66]. Glarborg et al [67] re-analyzed the experimental data from Glänzer and Troe [56], Hsu and Lin [64], and Zhang and Bauer [66], recommending the high-and low-pressure limiting rate coefficients proposed by Glänzer and Troe, together with a center-broadening factor of F cent,32 = 0.183.…”

Section: No X /Alkyl Reactionsmentioning

confidence: 92%

Sensitizing effects of NOx on CH4 oxidation at high pressure

Rasmussen

Glarborg

2008

Combustion and Flame

132

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Section: No X /Alkyl Reactionsmentioning

confidence: 92%

Sensitizing effects of NOx on CH4 oxidation at high pressure

Rasmussen

Glarborg

2008

Combustion and Flame

132

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“…Such effects have already been noted in the FID flames of benzene, toluene, and cyclohexane (10). This paper presents observations on the unburnt gases of an FID-type flame containing nitromethane, which are relevant to the pyrolysis (13)(14)(15) and hydrogenation of that compound, as well as to the mechanism of secondary ionization in cyanogenlhydrogen flames (8).…”

Section: Introductionmentioning

confidence: 71%

“…The formation of NO+ in the burnt gases of flames has been noted since the earliest work on flame ionization (2), and recently it has been closely associated with H,O+ (25). It may be that the reverse of the reaction [El is significant in the unburnt gases, with the HNO, being supplied from the nitromethane pyrolysis (13)(14)(15).…”

Section: Discussionmentioning

confidence: 99%

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Ionization of nitromethane in the flame ionization detector

McAllister¹,

Nicholson²,

Scott³

1981

Can. J. Chem.

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. Can. J. Chem. 59, 1819Chem. 59, (1981. The mass spectra observed on sampling the unburnt gases of a flame ionization detector to which nitromethane has been added are due mostly to proton transfer reactions of NH4+ and H30+. These are formed in the reaction zone from the primary ion HCO+, and pass through the unburnt gases to the sampling orifice. The ions which are detected may be attributed to pyrolysis (CH4NO+ and NO+) or hydrogenation products (CH2NH2+ and CH3NH2+) of nitromethane. The small amount of NO+ observed in the unburnt gases is attributed either to a primary ionization mechanism which produces NO+ from excited nitrogen atoms or molecules in the reaction zone, or to a reaction of H30+ with HNO,, a pyrolysis product of nitromethane. Observations of CH2NH2+ in the flame and in double resonance experiments performed in an ion cyclotron resonance mass spectrometer give limits on the proton affinity of methanimine (CH2NH) of 847.6-862.3 kJ mol-I. Chem. 59, 1819Chem. 59, (1981. Les spectres de masse d'echantillons de gaz qui n'ont pas brule dans un detecteur par ionisation a flamme auxquels on a ajoute du nitromethane sont dus principalement aux reactions de transfert de proton du NH4+ et du H30+. Ceux-ci se forment dans'la zone de reaction a partir de I'ion primaire HCO+ et sont vChicules, par les gazqui n'ont pas brule, dans I'orifice d'echantillonnage. Les ions qui sont dktectes peuvent etre attribues a la pyrolyse (CH4NO+ et NO+) ou aux produits d'hydrogenation (CH2NH2+ et CH3NH2+) du nitromethane. On attribue les faibles quantitks de NO+ observees dans les gaz qui n'ont pas brulk soit un mecanisme d'ionisation primaire qui produit du NO+ a partir des atomes d'azote excites ou des molCcules presentes dans la zone de reaction, soit a une reaction de H30+ avec HNO,, un produit de pyrolyse du nitromethane. Les ions CH2NH2+ observes dans la flamme ou dans des experiences de double resonance realisees dans un spectromktre de masse it resonance d'ion dans un cyclotron donnent des limites de l'affinite de la methanimine (CH2NH) pour le proton de 847,6-862,3 kJ mol-I.[Traduit par le journal] Introduction Studies of ions in flames have tended to concentrate on premixed flames of hydrocarbons (1-6), although some work has been done on ammonia and cyanogen flames (7,8). The flame ionization detector (FID) operates with a wide range of organic compounds and uses a small, conical, diffusion flame, in contrast to the large, flat, premixed flames employed in most of the recent studies. Investigations of the FID type of flame (9, 10) have shown the ionization mechanism is similar to that suggested for premixed flames (3), namely the reactions:

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“…He, N, or CIO had no effect (Ref. 704,732,765,769,773,785 Behavior is strongly affected by pressure, decomposition is complex (Ref. 719,720,730,731,739).…”

Section: (Chemical Propertiesmentioning

confidence: 99%

Compendium of Nitromethane Data Relevant to the Tactical Explosive System (TEXS) Program

Hershkowitz¹,

Dobratz²

1989

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The thermal decomposition of nitromethane under high pressure

Cited by 21 publications

References 3 publications

Sensitizing effects of NOx on CH4 oxidation at high pressure

Sensitizing effects of NOx on CH4 oxidation at high pressure

Ionization of nitromethane in the flame ionization detector

Compendium of Nitromethane Data Relevant to the Tactical Explosive System (TEXS) Program

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