Synthesis and Thermal Stability of Peroxy Alkyl Nitrates

Edney, Edward O.; Spence, John W.; Hanst, Philip L.

doi:10.1080/00022470.1979.10470857

Cited by 18 publications

(7 citation statements)

References 12 publications

(14 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…were assigned to be consistent with the reported data for CH302NO 2[Bahta et al, 1982] and C3H?O2NO2[Edney et al, 1979]. The photolysis constants for the 17 light sensitive species in the mechanism were calculated to simulate a clear sky at the solar zenith angles present on August 4 at the latitude and longitude of Los Angeles, California, the date and place of high [HONO] measurements made byPlatt et al.…”

supporting

confidence: 70%

The CH₃CHO‐NO₃ reaction and possible nighttime PAN generation

Cantrell¹,

Davidson²,

Busarow³

et al. 1986

J. Geophys. Res.

View full text Add to dashboard Cite

Kinetic studies have been made of the CH3CHO-NO 3 reaction in dilute mixtures of CH3CHO, NO•_, and N,_O5 in synthetic air at 700 torr and room temperature. During the course of the reaction, reactant and product analyses were made in situ, using long path length Fourier transform infrared spectroscopy. The major products of the reaction for these conditions are HONOr_ and CH3COO•_NO•_. All evidence suggests that the first step in the reaction sequence, NO 3 + CH3CHO• HONO,_ + CH3CO , proceeds with a rate constant, k = (2.1 + 0.4) x 10 -•5 ½m 3 molecule -• s -• at 299 + 1 K. These results, combined with other reaction rate data pertinent to tropospheric chemistry, are used to computer simulate the homogeneous chemistry of the polluted troposphere and to evaluate theoretically the nature of the nighttime chemistry. previous work. Hence the earlier conclusions as to the importance of (1) in the nighttime chemistry of the polluted troposphere must be questioned [Pitts et al., 1984]. However, recent measurements of the rate constant for the NO3-CH20 reaction by Cantrell et al. [1985] led to a value about a factor of 2 higher (k• = (6.3 _+ 1.1) x 10 -•6 cm -3 molecule -• s -1) than that of Atkinson et al. [1984]. Recently, Atkinson et al. [1984] also measured the NO3-CH3CHO rate constant and found k 2 = (1.34 +_ 0.28) x 10 -•s cm 3 molecule -• s -•. Both the k• and k 2 estimates are dependent upon the choice made for the equilibrium constant K 3. In view of the large differences observed in k• estimates to date, we felt that it is important to measure k 2 again as well.We report here on the results of our measurements and use these to judge, through computer simulations, the theoretical significance of (1) and (2) in the nighttime chemistry of the polluted troposphere. EXPERIMENTAL PROCEDURES Product AnalysisThe experimental techniques and laboratory equipment used in the present study have been discussed previously , and only a brief description need be given here. The large glass reaction cell (6.3-m length, 448-L volume) was equipped with a multiple-reflection, modified White optical system with a 5.31-m base path. In this work we employed 32 passes with a total optical path of 170 m. In each of the experiments, sufficient acetaldehyde (Fisher Scientific Reagent grade) and nitrogen dioxide (prepared from high-purity nitric oxide and ultra-high-purity oxygen, Linde) were added to the Chern., 88, 3095-3098, 1984.Tuesday, C. S., The atmospheric photooxidation of trans-butene-2

show abstract

supporting

confidence: 70%

The CH₃CHO‐NO₃ reaction and possible nighttime PAN generation

Cantrell¹,

Davidson²,

Busarow³

et al. 1986

J. Geophys. Res.

View full text Add to dashboard Cite

show abstract

“…PAN is readily separated from other gaseous components in the atmosphere by use of short nonpolar columns in gas chromatography.10 This sixmembered ring structure may also explain the increased stabilities of PANs when compared to their peroxyalkyl nitrate counterparts. 21 With regard to PAN atmospheric lifetimes, both pathways will have strong temperature dependences, with PAN lifetimes increasing with decreasing temperature.20 With respect to the equilibrium reaction 1, PAN's apparent lifetime will depend on the reactions which will sink the peroxyacetyl radical,2,20,21 with the known reactions being reaction with NO (see reaction 6), and the reaction with hydroperoxyl radical to form peroxyacetic The apparent lifetime of PAN will be determined by the NO/N02 ratio in the atmosphere for this loss mechanism as pointed out by Cox and Roffey,2 since the forward reaction in this case is rate limiting. PAN will have an atmospheric lifetime of ~80 min at an NO/N02 ratio of one, with the lifetime approaching infinity as [NO] goes to zero.…”

Section: Resultsmentioning

confidence: 99%

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

Senum¹,

Fajer²,

Gaffney³

1986

J. Phys. Chem.

View full text Add to dashboard Cite

“…For FC(O)O 2 radicals, the fluorocarbonyl peroxynitrate (FC(O)OONO 2 ) is a reservoir species. This interesting inorganic peroxide was first identified by IR spectroscopy, and the kinetics of its formation, the thermal stability, and the implications for the atmospheric chemistry have been investigated recently …”

Section: Introductionmentioning

confidence: 99%

Properties of Fluorocarbonyl Peroxynitrate

et al. 1997

View full text Add to dashboard Cite

The synthesis of FC(O)OONO2 is accomplished by the photolysis of a mixture of (FCO)2, NO2, and O2. The pure product is isolated after trap-to-trap condensation and the removal of byproducts by treatment of the crude product with O3 and AsF5. The colorless liquid freezes at −105 °C; its boiling point is 32 °C. At 20 °C and a few millibars, FC(O)OONO2 decomposes in the gas phase with a half-life of 20 h. FC(O)OONO2 is characterized by vapor pressure measurements, vibrational, 19F NMR, 13C NMR and UV spectroscopies as well as by mass spectrometry. According to the vibrational and NMR spectra, the compound exists at room temperature only as a syn conformer. The molecular structure of FC(O)OONO2 is determined by gas electron diffraction. The molecule possesses a skew structure with a dihedral angle of φ(COON) = 86.2(14)°. The short O−O bond (1.420(6) Å) and the long N−O bond (1.514(6) Å) are consistent with the chemical properties of this compound. The experimental geometry is reproduced reasonably well by quantum chemical.

show abstract

Synthesis and Thermal Stability of Peroxy Alkyl Nitrates

Cited by 18 publications

References 12 publications

The CH₃CHO‐NO₃ reaction and possible nighttime PAN generation

The CH₃CHO‐NO₃ reaction and possible nighttime PAN generation

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

Properties of Fluorocarbonyl Peroxynitrate

Contact Info

Product

Resources

About

Synthesis and Thermal Stability of Peroxy Alkyl Nitrates

Cited by 18 publications

References 12 publications

The CH3CHO‐NO3 reaction and possible nighttime PAN generation

The CH3CHO‐NO3 reaction and possible nighttime PAN generation

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

Properties of Fluorocarbonyl Peroxynitrate

Contact Info

Product

Resources

About

The CH₃CHO‐NO₃ reaction and possible nighttime PAN generation

The CH₃CHO‐NO₃ reaction and possible nighttime PAN generation