Thermal decomposition of nitrate esters

Hiskey, Michael A.; Brower, K. R.; Oxley, Jimmie C.

doi:10.1021/j100163a013

Cited by 106 publications

(72 citation statements)

References 17 publications

(22 reference statements)

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“…After heating ammonium nitrate in a 50/50 mix with mesitylene for 10 min at 300 o C, 2,4-dimethyl-benzonitrile and 2,4-dimethyl-benzaldehyde were detected in approximately equal yield. A 50/50 mixture of ammonium nitrate and tetralin heated under identical conditions produced naphthalene as the only detected organic product in contrast to its oxidation by NO 2 which also produced naphthalone [5]. The oxidation conditions during ammonium nitrate thermolysis are not rigorous enough to affect this oxidation.…”

Section: Pure Hydrocarbonsmentioning

confidence: 95%

Thermal decomposition of ammonium nitrate-based composites

1989

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To evaluate the thermal stability of ammonium nitrate-water-in-oil emulsions, the thermal decomposition kinetics and resultant products were examined. As a baseline, the thermal stability of ammonium nitrate with individual components of the emulsion was determined. Only mineral oil had any effect on the decomposition. Generally, ammonium nitrate mixed with hydrocarbons has enhanced thermal stability. However, ammonium nitrate mixed, rather than emulsified, with mineral oil can decompose along a lower energy pathway than pure ammonium nitrate. The extent of decomposition along that pathway is not large before the decomposition process results in emulsification of the ammonium nitrate and, thus, in termination of that pathway. Mineral oil appears to be unique among the hydrocarbons in its ability to destabilize ammonium nitrate. Experiments utilized differential scanning calorimetry in combination with conventional isothermal techniques.

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Section: Pure Hydrocarbonsmentioning

confidence: 95%

Thermal decomposition of ammonium nitrate-based composites

1989

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“…Many of the simple ANs are thermally stable, [31,32] and only slightly soluble in water, so their removal by thermal decomposition or wet deposition [33] is expected to be minor, but their dry deposition accounts for a percentage for methyl nitrate. [4] Photolysis and OH-initiated oxidations thus become the dominant sinks for ANs in the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Photochemical reactions of methyl and ethyl nitrate: a dual role for alkyl nitrates in the nitrogen cycle

Chen

Zhang

2011

Environ. Chem.

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Environmental context. Alkyl nitrates are considered to be important intermediates in the atmospheric hydrocarbons-nitrogen oxides-ozone cycle, which significantly determines air quality and nitrogen exchange between the atmosphere and the Earth's surfaces. The present laboratory study investigates reaction products of alkyl nitrates to elucidate their photochemical reaction mechanisms in the atmosphere. The results provide a better understanding of the role played by alkyl nitrates in the atmospheric environment.Abstract. Alkyl nitrates (ANs) are important nitrogen-containing organic compounds and are usually considered to be temporary reservoirs of reactive nitrogen NO x (NO 2 and NO) in the atmosphere, although their atmospheric fates are incompletely understood. Here a laboratory study of the gas-phase photolysis and OH-initiated reactions of methyl nitrate (CH 3 ONO 2 ) and ethyl nitrate (C 2 H 5 ONO 2 ), as models of atmospheric ANs, is reported with a focus on elucidating the detailed photochemical reaction mechanisms of ANs in the atmosphere. A series of intermediate and end products were well characterised for the first time from the photochemical reactions of methyl and ethyl nitrate conducted under simulated atmospheric conditions. Notably, for both the photolysis and OH-initiated reactions of CH 3 ONO 2 and C 2 H 5 ONO 2 , unexpectedly high yields of HNO 3 (photochemically non-reactive nitrogen) were found and also unexpectedly high yields of peroxyacyl nitrates (RC(O)OONO 2 , where R ¼ H, CH 3 , CH 3 CH 2 ,y) (reactive nitrogen) have been found as CH 3 C(O)OONO 2 in the C 2 H 5 ONO 2 reaction or proposed as HC(O)OONO 2 in the CH 3 ONO 2 reaction. Although the yields of HNO 3 from the ANs under ambient conditions are likely variable and different from those obtained in the laboratory experiments reported here, the results imply that the ANs could potentially serve as a sink for reactive nitrogen in the atmosphere. The potential for this dual role of organic nitrates in the nitrogen cycle should be considered in the study of air quality and nitrogen exchange between the atmosphere and surface. Finally, an attempt was made to estimate the production of HNO 3 and peroxyacyl nitrates derived from NO x by ANs as intermediates in the atmosphere.

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“…As per Hiskey et al [34], butylaldehyde is also highly reactive in acidic medium. It may react with nitrogen dioxide to yield carbon monoxide, nitric oxide, and water vapor as…”

Section: A Possible Mechanism For Thermal Decomposition Of Nitrated Tbpmentioning

confidence: 68%

“…The effect of concentration and temperature on the decomposition of equilibrated TBP has been studied. A detailed reaction mechanism for thermal decomposition of TBP-nitric acid was proposed on the basis of reaction products profile [29][30][31][32][33][34][35]. The data generated in these experiments can be useful to analyse pitfalls of vitrification process of radioactive waste after extraction process, namely, UREX, PUREX.…”

Section: Introductionmentioning

confidence: 99%

Thermal Decomposition of Nitrated Tri-n-Butyl Phosphate in a Flow Reactor

Patil

Gaikar

Kumar

et al. 2012

ISRN Chemical Engineering

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Tri-n-butyl phosphate (TBP) is a universal nuclear extractant, commercially used in the PUREX process for the last 60 years. However, it is prone to nitration and thermal degradation, and as a consequence a red-oil event may be initiated under several operating conditions resulting in severe pressurization of vessel/cell if venting is inadequate. In this work, an attempt was made to understand the reaction pathway of thermal decomposition of nitrated TBP in a flow reactor at atmospheric pressure. Many reaction products were identified and quantified by instrumental methods like HPLC-RI and GC-TCD. The experimental data was analysed with a power law model and the apparent rate constants were estimated. The activation energy for thermal decomposition of nitrated TBP, assuming an Arrhenius type of temperature dependency, was estimated to be 47.39 ± 0.25 kJ·mol −1 . The effect of both varying temperature and concentration of nitric acid on conversion of TBP into degradation products and products distribution was experimentally studied. Based on the experimental observations, a reaction mechanism framework for thermal decomposition of nitrated TBP is proposed.

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Thermal decomposition of nitrate esters

Cited by 106 publications

References 17 publications

Thermal decomposition of ammonium nitrate-based composites

Thermal decomposition of ammonium nitrate-based composites

Photochemical reactions of methyl and ethyl nitrate: a dual role for alkyl nitrates in the nitrogen cycle

Thermal Decomposition of Nitrated Tri-n-Butyl Phosphate in a Flow Reactor

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