A smog chamber and modeling study of the gas phase NOx–air photooxidation of toluene and the cresols

An experimental and modeling study of irradiated toluene–NO_x–air, toluene–benzaldehyde–NO_x–air, and cresol–NO_x–air mixtures at part-per-million concentrations has been carried out. These mixtures were irradiated at 303 ± 1 K in a 5800-liter Teflon-lined, evacuable environmental chamber, with temperature, humidity, light intensity, spectral distribution, and the concentrations of O₃, NO, NO₂, toluene, PAN, formaldehyde, benzaldehyde, o-cresol, m-nitrotoluene, and methyl nitrate beingmonitored as a function of time. For the toluene and toluene–benzaldehyde–NO_x–air runs a variety of initial reactant concentrations were investigated. Cresol–NO_x–air runs were observed to be much less reactive in terms of O₃ formation and NO to NO₂ conversion rates than toluene–NO_x–air runs, with the relative reactivity of the cresol isomers being in the order meta » ortho > para. The addition of benzaldehyde to toluene–NO_x–air mixtures decreased the reactivity, in agreement with previous studies. Alternative mechanistic pathways for the NO_x photooxidations of aromaticsystems in general are discussed, and the effects of varying these mechanistic alternatives on the model predictions for the toluene and o-cresol–NO_x–air systems are examined. Fits of the calculations to most of the experimental concentration–time profiles could be obtained to within the experimental uncertainty for two of the mechanistic options considered. In both cases it is assumed that (1) O₂ adds to the OH–toluene adduct ～75% of the time forming, after a further addition of O₂, a C₇ bicyclic peroxy radical, and (2) this C₇ bicyclic peroxy radical reacts with NO ～75% of the time to ultimately form α-dicarbonyls and conjugated γ-dicarbonyls (e.g., methylglyoxal + 2-butene-1,4-dial) and ～25% of the time to form organic nitrates. The major uncertainties in the mechanisms concern (1) the structure of the bicyclicperoxy intermediate, and (2) the γ-dicarbonyl photooxidation mechanism. Good fits to the o-cresol concentration–time profiles in the toluene–NO_x runs are obtained if it is assumed that o7-cresol reacts rapidly with NO₃ radicals. However, it is observed that the model underpredicts nitrotoluene yields by a factor of ～10, but this is in any case a minor product. It is concluded that further experimental work will be required toadequately validate the assumptions incorporated in the aromatic photooxidation mechanisms presented here.     

Observation of diffractive b-quark production at the fermilab tevatron

We report a measurement of the fraction of b quarks produced diffractively in &pmacr;p collisions at sqrt[s] = 1.8 TeV. Diffraction is identified by the absence of particles in a forward pseudorapidity region. From events with an electron of transverse momentum 9.5相似文献   

Analysis of dinitrofluoranthenes by high resolution capillary gas chromatography/mass spectrometry

This paper reports the retention indices of eighteen of the possible twenty-five dinitrofluoranthene isomers.     

Gas phase reaction of NO2 with alkenes and dialkenes

The kinetics of the gas phase reactions of NO₂ with a series of organics have been studied at 295 ± 2 K. It was observed that only 2,3-dimethyl-2-butene and the conjugated dialkenes studied reacted at observable rates, with rate constants which ranged from 1.5 × 10^?20 cm³ molecule^?1 s^?1 for 2,3-dimethyl-2-butene to 1.3 × 10^?17 cm³ molecule^?1 s^?1 for α-phellandrene. These rate constants are compared with the available literature data and the mechanisms of these reactions are discussed.     

An investigation of the dark formation of nitrous acid in environmental chambers

The formation of nitrous acid (HONO) in the dark from initial concentrations of NO₂ of 0.1–20 ppm in air, and the concurrent disappearance of NO₂, were monitored quantitatively by UV differential optical absorption spectroscopy in two different environmental chambers of ca.4300- and 5800-L volume (both with surface/volume ratios of 3.4 m^?1). In these environmental chambers the initial HONO formation rate was first order in the NO₂ concentration and increased with the water vapor concentration. However, the HONO formation rate was independent of the NO concentration and relatively insensitive to temperature. The initial pseudo-first-order consumption rate of NO₂ was (2.8 ± 1.2) × 10^?4 min^?1 in the 5800-L Teflon-coated evacuable chamber and (1.6 ± 0.5) × 10^?4 min^?1 in a 4300-L all-Teflon reaction chamber at ca.300 K and ca.50% RH. The initial HONO yields were ca.40–50% of the NO₂ reacted in the evacuable chamber and ca.10–30% in the all-Teflon chamber. Nitric oxide formation was observed during the later stages of the reaction in the evacuable chamber, but ca.50% of the nitrogen could not be accounted for, and gas phase HNO₃ was not detected. The implications of these data concerning radical sources in environmental chamber irradiations of NO_x? organic-air mixtures, and of HONO formation in polluted atmospheres, are discussed.     

Atmospheric reactions of chloroethenes with the OH radical

The kinetics and products of the homogeneous gas-phase reactions of the OH radical with the chloroethenes were investigated at 298 ± 2 K and atmospheric pressure. Using a relative rate technique and ethane as a scavenger for the chlorine atoms produced in these OH radical reactions, rate constants (in units of 10^?12 cm³ molecule^?1s^?1) of 8.11 ± 0.24, 2.38 ± 0.14, and 1.80 ± 0.03 were obtained for 1,1-dichloroethene, cis-1, 2-dichloroethene and trans-1,2-dichloroethene, respectively. Under these conditions, the major products observed by long pathlength FT-IR absorption spectroscopy were HCHO and HC(O)Cl from vinyl chloride; HC(O)Cl from cis- and trans-1,2-dichloroethene; HCHO and COCl₂ from 1,1-dichloroethene; HC(O)Cl and COCl₂ from trichloroethene; and COCl₂ from tetrachloroethene. In the absence of a Cl atom scavenger, significant yields of the chloroacetyl chlorides, CH_xCl_3?xC(O)Cl, were observed from 1,1-dichloro-, trichloro- and tetrachloroethene, indicating that these products resulted from reactions involving chlorine atoms. The yields of all of these products are reported and the mechanisms of these gas-phase reactions discussed. In addition, OH radical reaction rate constants were redetermined, in the presence of a Cl atom scavenger, for cis- and trans-1,3-dichloropropene and 3-chloro-2-chloromethyl-1-propene, being (in units of 10^?12 cm³ molecule^?1 s^?1) 8.45 ± 0.41, 14.4 ± 0.8, and 33.5 ± 3.0, respectively.     

Long pathlength differential optical absorption spectroscopy (D O A S) measurements of gaseous HONO,NO2 and HCNO in the California South Coast Air Basin

A differential optical absorption spectrometer (DOAS) system was operated at Long Beach, CA during the 1987 SCAQS Fall episodes to measure atmospheric concentrations of nitrous acid (HONO), as well as ambient levels of nitrogen dioxide (NO₂) and formaldehyde (HCHO). The rapid scanning (-3000 spectra per min) spectrometer was interfaced to a 25 m basepath open, multiple reflection system operated routinely at a total optical path of 800 m. During several of the Fall episodes at Long Beach, levels of gaseous HONO were the highest (>15 ppb) reported to date by the DOAS technique. Although approximately half, to all, of the measured nighttime HONO concentrations could be accounted for by proposed heterogeneous formation pathways involving NO₂, HONO concentrations correlated well with primary pollutants such as CO and NO, suggesting that elevated nighttime HONO concentrations in the western end of the Los Angeles basin may be influenced by emissions of HONO from combustion sources. This has significant implications for models which assume HONO arises only from secondary formation, rather than a combination of direct emissions and atmospheric reactions. Estimates of hydroxyl (OH) radical production show that photolysis of HONO shortly after sunrise on these episode days produces a large pulse of OH radicals at a time of the day when OH production from photolysis of O₃ and HCHO is low. In terms of integrated OH radical production, HONO is of comparable importance to HCHO and much more important than O₃ during these Fall periods.     

Evidence for alkoxy radical isomerization in photooxidations of C4C6 alkanes under simulated atmospheric conditions

We have calculated approximate room temperature rate constants for intramolecular hydrogen shift isomerizations of alkyl, alkoxy and alkylperoxy radical intermediates in photochemical smog and found that alkoxy radicals with δ hydrogens appear to undergo 1,5 hydrogen shifts at ambient conditions. Product distributions observed during irradiations of alkane (n-butane, n-pentane and n-hexane)NO_xair systems in two quite-different ≈6000-liter environmental chambers were found to be consistent with this prediction. For example, in the n-pentaneNO _xair system the observed large yields of 3-pentanone relative to 2-pentanone were consistent with room temperature rate constants which we have estimated for the corresponding hydrogen shift isomerizations. While such isomerizations have been well recognized in studies of free radicals and high temperature hydrocarbon oxidations, they are not taken into account in current kinetic mechanisms for alkane oxidation under ambient atmospheric conditions. This has implications for the construction of computer models of photo-chemical smog formation.