Photochemical synthesis of peroxyacyl nitrates in gas phase via chlorine-aldehyde reaction

Gay, Bruce W.; Noonan, Richard C.; Bufalini, Joseph J.; Hanst, Philip L.

doi:10.1021/es60112a006

Cited by 55 publications

(12 citation statements)

References 6 publications

(8 reference statements)

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“…A widely used method for the in situ production of PAN-like compounds is the Cl-atom initiated oxidation of an appropriate aldehyde precursor in air in an excess of NO 2 [Gay et al, 1976] in a reaction sequence analogous to that presented in reaction scheme I. In the case of the pinonaldehyde molecule, several H atoms other than the aldehydic H atom can also be abstracted by the C1 atom, leading to a mixture of different products.…”

Section: Methods For In Situ Production Of C•p-panmentioning

confidence: 99%

Evidence for formation of a PAN analogue of pinonic structure and investigation of its thermal stability

Nozière¹,

Barnes²

1998

J. Geophys. Res.

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Abstract. The first evidence and laboratory study of a peroxyacetyl nitrate (PAN) analogue produced by the photooxidation of a terpene, c•-pinene, is presented. This PAN analogue, assigned to 3-acetyl-2,2-dimethyl-cyclobutane-acetyl peroxynitrate and referred to as "c•-pinonyl peroxynitrate" (c•P-PAN) was synthesized in the gas phase from the radical (OH, C1, Br, or NO3) initiated oxidation of pinonaldehyde (3-acetyl-2,2-dimethylcyclobutyl-ethanal) in the presence of excess NO 2 and evidenced by Fourier transform- In the present study a method for the in situ gas-phase synthesis of aP-PAN from different radical sources and characterization of its IR spectrum is presented. In particular, experiments on the reaction of pinonaldehyde with OH radicals have been performed in order to establish the fate of this compound in the troposphere in NOx-rich environments. Finally, results are also reported from a kinetic investigation of the thermal stability of aP-PAN and the atmospheric chemistry of pinonaldehyde and aP-PAN are discussed. Experimental Method Method for In Situ Production of c•P-PANA widely used method for the in situ production of PAN-like compounds is the Cl-atom initiated oxidation of an appropriate aldehyde precursor in air in an excess of NO 2 [Gay et al., 1976] in a reaction sequence analogous to that presented in reaction scheme I. In the case of the pinonaldehyde molecule, several H atoms other than the aldehydic H atom can also be abstracted by the C1 atom, leading to a mixture of different products. In order to establish the cleanest source for c•P-PAN, i.e., the source most selective toward the aldehydic group, a series of experiments with different radical initiators (OH, C1, NO3, and Br) was performed.The reactions were carried out in a 1080-1 quartz reactor using in situ long path FT-IR spectroscopy (BRUKER IFS 88 spectrometer equipped with an MCT detector) to monitor reactants and products. The optical pathlength was 484.7 m and a spectral resolution of 1 cm-• was used. For the reactions

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Section: Methods For In Situ Production Of C•p-panmentioning

confidence: 99%

Evidence for formation of a PAN analogue of pinonic structure and investigation of its thermal stability

Nozière¹,

Barnes²

1998

J. Geophys. Res.

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“…17 The syntheses were carried out by the chlorine initiation method previously reported. 18 The chlorine, nitrogen dioxide, and hydrocarbon gases were taken from lecture bottles. The infrared spectra confirmed the purity of the reactants.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Thermal Stability of Peroxy Alkyl Nitrates

Edney¹,

Spence²,

Hanst³

1979

Journal of the Air Pollution Control Association

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“…The formation of PFN in the irradiation of a HCHO þ NO 2 þ Cl system in air was assumed by Gay et al based on IR spectra, [54] but this was later corrected to be peroxy nitric acid by Hanst and Gay. [55] We could not identify PFN by FTIR spectroscopy because of the lack of its standard spectrum.…”

mentioning

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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Photochemical synthesis of peroxyacyl nitrates in gas phase via chlorine-aldehyde reaction

Cited by 55 publications

References 6 publications

Evidence for formation of a PAN analogue of pinonic structure and investigation of its thermal stability

Evidence for formation of a PAN analogue of pinonic structure and investigation of its thermal stability

Synthesis and Thermal Stability of Peroxy Alkyl Nitrates

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

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