Fourier transform infrared spectroscopic study of the thermal stability of peroxyacetyl nitrate

Senum, G.; Fajer, R.; Gaffney, J. S.

doi:10.1021/j100273a034

Cited by 53 publications

(35 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Laboratory investigations have indicated that thermal decomposition is the predominant removal pathway of PAN in the daytime (Roberts and Bertman, 1992;Senum et al, 1986;Grosjean et al, 2001), because its reaction rate with OH radical (Wallington et al, 1984) and its photolysis are slow (Senum et al, 1984) as well as the low wet deposition rate (Gaffney et al, 1987). From the reactions (R2, R-2, and R3) illustrated in Section 3.3, the PAN lost by thermal decomposition (TPAN) is given by Equation (1).…”

Section: Major Sink Of Pan: Thermal Decompositionmentioning

confidence: 99%

Summertime distributions of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) in Beijing: Understanding the sources and major sink of PAN

Zhang

Li-hua

et al. 2015

Atmospheric Environment

View full text Add to dashboard Cite

a b s t r a c tPeroxyacetyl nitrate (PAN), a major secondary pollutant in the atmosphere, has received much concern for its particular importance in atmospheric chemistry and adverse effects on human and plants. Atmospheric PAN and PPN were measured by using a gas chromatograph equipped with electron capture detector (GC-ECD) from June to September 2010, and the source and major sink for PAN were firstly studied in Beijing. The distinct diurnal variations of PAN and PPN with maximum in the afternoon were observed, and the mean and maximum values were 2.61 ± 2.57 ppbv (N ¼ 839) and 12.5 ppbv for PAN and 0.52 ± 0.38 ppbv (N ¼ 152) and 2.16 ppbv for PPN during the measuring period, respectively. Good correlation (R ¼ 0.85) between PAN and PPN with a slope (DPPN/DPAN) of 0.134 indicated that anthropogenic volatile organic compounds (AVOCs) dominated the photochemical formation of PANs in Beijing. Further, we found acetaldehyde was the predominant carbonyl precursor of PAN with the contribution of 59.7% to the total peroxyacetyl (PA) radical. Methyl glyoxal, methacrolein, acetone, methyl vinyl ketone, and biacetyl contributed 7.1%, 8.8%, 19.7%, 3.4%, and 1.3% to total PA radical, respectively. Anti-correlation between PAN concentrations and the NO/NO 2 ratios was found during the whole investigating period. In addition, the amount of PAN lost by thermal decomposition (TPAN) accounted for remarkable fractions of PAN observed under high temperature during both daytime and nighttime.

show abstract

Section: Major Sink Of Pan: Thermal Decompositionmentioning

confidence: 99%

Summertime distributions of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) in Beijing: Understanding the sources and major sink of PAN

Zhang

Li-hua

et al. 2015

Atmospheric Environment

View full text Add to dashboard Cite

show abstract

“…While all calculated rates comprise a range of (10\ }0.4 pptv h\ , most of them ('75%) were in the much narrower range of 10\ }10\ pptv h\ . Assuming a mean rate of 2); the black line corresponds to simulated methyl formation rates using reaction rate constant given by Senum et al (1986). 5;10\ pptv h\ during the day with a sun shine duration of 12 h, a total decay of 0.6 pptv d\ may be estimated. This decay is equivalent to the concurrent NO V production because one additional NO molecule is formed during the decay of a PAN molecule.…”

Section: Pan Lifetimesmentioning

confidence: 99%

“…The appearance of methyl nitrate in the atmosphere has been at least partly attributed to a uni-molecular cyclic decomposition of PAN (Stephens, 1969;Senum et al, 1986;Roberts, 1990) due to the reaction…”

Section: Pan Lifetimesmentioning

confidence: 99%

“…Although this pathway has been proven to be much less important than it once was thought to be, and may not occur at all (Orlando et al, 1992;Roumelis and Glavas, 1992), we used the rate coe$cient reported by Senum et al (1986) to derive an upper limit for the methyl nitrate formation. The calculated PAN decay rates equivalent to the methyl nitrate formation rates are shown in Fig.…”

Section: Pan Lifetimesmentioning

confidence: 99%

See 1 more Smart Citation

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Jacobi

Weller

Jones

et al. 2000

Atmospheric Environment

View full text Add to dashboard Cite

Because investigations of PAN at higher southern latitudes are very scarce, we measured surface PAN concentrations for the "rst time in Antarctica. During the Photochemical Experiment at Neumayer (PEAN'99) campaign mean surface PAN mixing ratios of 13$7 pptv and maximum values of 48 pptv were found. When these PAN mixing ratios were compared to the sum of NO V and inorganic nitrate they were found to be equal or higher. Low ambient air temperatures and low PAN concentrations caused a slow homogeneous PAN decomposition rate of approximately 5;10\ pptv h\ . These slow decay rates were not su$cient to "rmly establish the simultaneously observed NO V concentrations. In addition, low concentration ratios of [HNO ]/[NO V ] imply that the photochemical production of NO V within the snow pack can in#uence surface NO V mixing ratios in Antarctica. Alternate measurements of PAN mixing ratios at two di!erent heights above the snow surface were performed to derive #uxes between the lower troposphere and the underlying snow pack using calculated friction velocities. Most of the concentration di!erences were below the precision of the measurements. Therefore, only an upper limit for the PAN #ux of $1;10 molecules m\ s\ without a predominant direction can be estimated. However, PAN #uxes below this limit can still in#uence both the transfer of nitrogen compounds between atmosphere and ice, and the PAN budget in higher southern latitudes.

show abstract

“…Methyl nitrate is the simplest analog of this series, and is one of the dominant nitrate products from organic photooxidations. Methyl nitrate has been shown to be the dominant product from the thermal decomposition of peroxyacetyl nitrate as well [8]. Methyl nitrate has been found to have a low solubility in water and to undergo hydrolysis at a negligible rate in moderately acidic aqueous 400 GAFFNEY ET AL.…”

Section: Introductionmentioning

confidence: 99%

Measurement of the reactivity of OH with methyl nitrate: Implications for prediction of alkyl nitrate‐OH reaction rates

Gaffney

Fajer

Senum

et al. 1986

Int J of Chemical Kinetics

Self Cite

View full text Add to dashboard Cite

The rate of the gas phase reaction of hydroxyl radical with methyl nitrate has been measured to be (3.4 * 0.4) x cm3 molecule-' s-' at 298 K using flow discharge/ resonance fluorescence techniques. By means of correlation methods, this rate determination is used to predict a vertical ionization potential of 12.6 eV, a bond dissociation energy for H-CH20N02 of 101 kcal mol-', and a rate for O?P) reaction with methyl nitrate of ca. 9 x cm3 molecule-' s-'. In conjunction with previously derived relative data for reaction of alkyl nitrates with OH radical in the gas phase, a priori estimated reactivities for 1-, 2-, and 3-positionally substituted straight chain alkyl nitrates have been reexamined. Revised reactivities for OH abstraction of specific hydrogens substituted on straight chain alkyl nitrates are presented and discussed, and an atmospheric lifetime of ca. 2 yrs is estimated for methyl nitrate removal due to OH.

show abstract

Fourier transform infrared spectroscopic study of the thermal stability of peroxyacetyl nitrate

Cited by 53 publications

References 6 publications

Summertime distributions of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) in Beijing: Understanding the sources and major sink of PAN

Summertime distributions of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) in Beijing: Understanding the sources and major sink of PAN

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Measurement of the reactivity of OH with methyl nitrate: Implications for prediction of alkyl nitrate‐OH reaction rates

Contact Info

Product

Resources

About