Generation of peroxy radicals from peroxy nitrates (RO2NO2). Decomposition of peroxyacyl nitrates

Hendry, Dale G.; Kenley, Richard A.

doi:10.1021/ja00451a073

Cited by 98 publications

(53 citation statements)

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“…Yet it is unreasonable to assume that RO2 and NO2 do not react. Therefore, we assume that they react analogously to the reasonably well understood RC03 + NO2 [59,61] and HO:! + NO2 [50] systems, except that, unlike acylperoxy nitrates, alkylperoxy nitrates are assumed to decompose back to RO2 + NO2 sufficiently rapidly so that buildup of R02N02 is insignificant, and thus there is no net reaction.…”

Section: Other Peroxy Radical Reactionsmentioning

confidence: 99%

“…Based on thermochemical estimates 1901, these reactions can be estimated, using techniques similar to those of Baldwin and co-workers [7], to be significantly faster than competing bimolecular processes under these conditions. [59] obtain a ratio of 3 from the decomposition of PAN in the presence of NO and NO*. However, experimental details are not given.…”

Section: Nates For Reaction List In Appendixmentioning

confidence: 99%

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Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n‐butane in photochemical smog

Carter

Lloyd

Sprung

et al. 1979

Int J of Chemical Kinetics

161

153

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A detailed mechanism is presented far reactions occurring during irradiation of part-permillion concentrations of propene and/or n-butane and oxides of nitrogen in air. Data from an extensive series of well-characterized smog chamber experiments carried out in our 5800-liter evacuable chamber-solar simulator facility designed for providing data suitable for quantitative model validation were used to elucidate several unknown or uncertain kinetic parameters and details of the reaction mechanism.The mechanism was then tested against the data base from the smog chamber runs. In general, most calculated concentration-time profiles agreed with experiments to within the experimental uncertainties. Fits were usually attained to within f20% or better for ozone, NO, propene, and n-butane, to within -+30% or better for NOz, PAN, methyl ethyl ketone, 2-butyl nitrate, butyraldehyde, and (in runs not containing propene) methyl nitrate, to within --f50% or better for the minor products 1-butyl nitrate and propene oxide, and to within a factor of 2 for methyl nitrate in propene-containing runs. Propionaldehyde was consistently underpredicted in all runs; it is probably a chamber contaminant. For formaldehyde and acetaldehyde, the major products in both systems, fits to within -420% were often obtained, yet for a number of experiments, significantly greater discrepancies were observed, probably as a result of experimental and/or analytical problems.The good fits to experimental data were attained only after adjusting several rate constants or rate constant ratios related to uncertainties concerning chamber effects or the chemical mechanism. The largest uncertainty concerns the necessity to include in the mechanism a significant rate of radical input from unknown sources in the smog chamber. Other areas where fundamental kinetic and mechanistic data are most needed before a predictive, detailed propene + n-butane-NO,-air smog model can be completely validated concern other chamber effects, the 03 + propene mechanism, decomposition rates of substituted alkoxy radicals, CARTER E T AL.primary quantum yields for radical production as a function of wavelength for aldehyde and ketone photolyses, and the mechanisms and rates of reactions of peroxy radicals with NO and NOz.

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Section: Other Peroxy Radical Reactionsmentioning

confidence: 99%

Section: Nates For Reaction List In Appendixmentioning

confidence: 99%

Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n‐butane in photochemical smog

Carter

Lloyd

Sprung

et al. 1979

Int J of Chemical Kinetics

161

153

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“…Values for this ratio of 1.7 and 3.1 were taken from studies of PAN reported in the literature. 21 ' 22 Using the average of these two values gives the following Arrhenius expression:…”

Section: Decomposition Ratementioning

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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“…Recently, a thermal dissociation-chemical ionization mass spectrometry (TD-CIMS) method was developed by Slusher et al (2004). The method utilizes iodide anion as the primary ion to react with PA radicals that are produced from the thermal dissociation of PAN (Cox and Roffey, 1977;Hendry and Kenley, 1977;Roberts and Bertman, 1992). The resulting acetate anion is then detected through a quadrupole mass spectrometer as a measurement of PAN.…”

Section: Introductionmentioning

confidence: 99%

Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere

et al. 2011

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Abstract. This paper presents a detailed laboratory characterization of a thermal dissociation chemical ionization mass spectrometer (TD-CIMS) for the atmospheric measurement of Peroxyacetyl nitrate (PAN) and its homologues (PANs). PANs are efficiently dissociated in a heated inlet and the resulting peroxy acyl radicals are reacted with I − ions in a flow tube. The mass spectrometer detects the corresponding carboxylate ions. PAN, peroxypropionyl nitrate (PPN), peroxyisobutyryl nitrate (PiBN), peroxy-n-butyryl nitrate (PnBN), peroxyacryloyl nitrate (APAN), peroxycrotonyl nitrates (CPAN) and peroxymethacryloyl nitrate (MPAN) were cross-calibrated with both a dual channel GC/ECD and a total odd-nitrogen (NO y ) instrument for the NCAR TD-CIMS' typical aircraft operation conditions. In addition, the instrument sensitivity to a number of more exotic PANs (peroxyhydroxyacetyl nitrate, methoxyformyl peroxynitrate, and peroxybenzoyl nitrate) was evaluated qualitatively by comparisons with a long-path FTIR instrument.The sensitivity for PPN is slightly higher than that of PAN. Larger aliphatic and olefinic PAN compounds generally showed lower sensitivities. We postulate that these differences are owing to secondary reactions in the thermal decomposition region, which either reduce the yield of peroxy acyl radicals or cause losses of these radicals through intramolecular decomposition. The relative importance of these secondary reactions varies considerably between different PAN species.Correspondence to: F. M. Flocke (ffl@ucar.edu)Results also indicate that the reaction of the larger peroxy acyl radicals with the ion-water cluster, I − (H 2 O)n proceeds about an order of magnitude faster than with I − alone, as has been observed for peroxy acetyl radicals. Sensitivity variations among the individual PAN species at very low water vapor were observed. The results call for careful evaluation of each PAN species to be measured and for each desired operating condition of a TD-CIMS instrument.

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Generation of peroxy radicals from peroxy nitrates (RO2NO2). Decomposition of peroxyacyl nitrates

Cited by 98 publications

References 0 publications

Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n‐butane in photochemical smog

Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n‐butane in photochemical smog

Synthesis and Thermal Stability of Peroxy Alkyl Nitrates

Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere

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