The Chemistry of Nitrate Esters

Boschan, Robert H.; Merrow, Raymond T.; Dolah, Robert W. Van

doi:10.1021/cr50003a001

Cited by 203 publications

(136 citation statements)

References 55 publications

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“…Such reaction often called carbonyl elimination, E CO 2 ( Baker and Heggs, 1955), is enhanced by the availability of acidic hydrogen on the two primary Cs in NG. Whereas the formation of NO À 3 was possibly caused by a b-hydrogen elimination and/or by substitution of OH À at the secondary C in NG as commonly seen in secondary alkyl nitrates (Baker and Easty, 1952;Boschan et al, 1955). In the present study the ratio of nitrite to nitrate calculated from Table 1 in the presence and absence of microwave heating was 2.5 and 2.8, respectively.…”

Section: Hydrolysis Pathways Of Ngsupporting

confidence: 47%

“…The use of excess amounts of reactants in these methods creates another disposal problem. Few other academic research articles have been reported on the hydrolysis of NG (Boschan et al, 1955;Capellos et al, 1984;Tsaplev, 2004), but little information is available on the eventual fate of the nitrate ester. To provide answers to these questions and to gain new insights into the degradation pathway of NG we studied the hydrolysis of the (Walter et al, 1997;Srogi, 2006) and to conduct organic synthesis (Gedye et al, 1991;Clarke et al, 2007).…”

Section: Introductionmentioning

confidence: 99%

“…Earlier literatures show that NG can be hydrolyzed under high alkaline conditions (pH P 12) to produce formate, oxalate, acetate often with a poor mass balance (Boschan et al, 1955;Capellos et al, 1984;Tsaplev, 2004). The use of mild alkaline conditions assisted with microwave irradiation were selected here because, (1) pH 9 is closer to natural environmental conditions found in contaminated soil and water, and (2) rapid hydrolysis by microwave can lead to the formation of intermediates in sufficient amounts that would allow detection thereby helping to gain more insights into the NG decomposition pathway(s).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Microwave-assisted hydrolysis of nitroglycerin (NG) under mild alkaline conditions: New insight into the degradation pathway

Halasz

Thiboutot²,

Ampleman³

et al. 2010

Chemosphere

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Section: Hydrolysis Pathways Of Ngsupporting

confidence: 47%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Microwave-assisted hydrolysis of nitroglycerin (NG) under mild alkaline conditions: New insight into the degradation pathway

Halasz

Thiboutot²,

Ampleman³

et al. 2010

Chemosphere

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“…1a and b), and nitric acid (m / z − 62) is formed via radical reactions in the gas-phase system of glyoxal-NO (Boschan et al, 1955) and oxidizes some hydroxyl groups (Connelly et al, 2012). Therefore, m / z − 147 and 226 are organonitrates formed by the aqueous-phase reaction of glyoxal and nitric acid.…”

Section: Photochemical Organonitrate Formation In Wet Aerosolsmentioning

confidence: 99%

Photochemical organonitrate formation in wet aerosols

Lim

Kim

et al. 2016

Atmos. Chem. Phys.

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Abstract. Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal-and OH-containing ammonium sulfate or sulfuric acid particles in the presence of NO x and O 3 at high and low relative humidity. Particles were analyzed using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS).During the 3 h irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen sulfates (CHNOS). These were also the dominant products formed in the dark chamber, indicating non-radical formation. In the humid chamber (> 70 % relative humidity, RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m / z − 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NO x and OH during the irradiation.

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“…Nucleophilic substitution reactions of water and ON molecules to give alcohols and nitric acid (reaction (2)) has been suggested as the major reaction pathway (Boschan et al 1955). Baker and Easty (1952) studied kinetics of neutral hydrolysis in bulk solution using methyl, ethyl, isopropyl, and tert-butyl nitrates at 60 to 100 • C. Their results suggest that the hydrolysis rate of tert-butyl nitrate is 10 4 -10 5 times faster than those of primary and secondary nitrates.…”

mentioning

confidence: 99%

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Liu

Shilling

Song

et al. 2012

Aerosol Science and Technology

183

204

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Organonitrate (ON) groups are thought to be important substituents in secondary organic aerosols (SOAs). Model simulations and laboratory studies indicate a large fraction of ON groups in aerosol particles, but much lower quantities are observed in the atmosphere. Hydrolysis of ON groups in aerosol particles has been proposed recently to account for this discrepancy. To test this hypothesis, we simulated formation of ON molecules in a reaction chamber under a wide range of relative humidity (RH) (0 to 90%). The mass fraction of ON groups (5 to 20% for high-NO x experiments) consistently decreased with increasing RH, which was best explained by hydrolysis of ON groups at a rate of 4 day −1 (lifetime of 6 h) for reactions under RH greater than 20%. In addition, we found that secondary nitrogen-containing molecules absorb light, with greater absorption under dry and high-NO x conditions. This work provides the first evidence for particle-phase hydrolysis of ON groups, a process that could substantially reduce ON group concentration in atmospheric SOAs.

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The Chemistry of Nitrate Esters

Cited by 203 publications

References 55 publications

Microwave-assisted hydrolysis of nitroglycerin (NG) under mild alkaline conditions: New insight into the degradation pathway

Microwave-assisted hydrolysis of nitroglycerin (NG) under mild alkaline conditions: New insight into the degradation pathway

Photochemical organonitrate formation in wet aerosols

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

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