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  • modelling  (1)
  • rate constant  (1)
  • 1
    ISSN: 1573-0662
    Keywords: air pollution ; field study ; modelling ; atmospheric chemistry ; troposphere ; clouds ; nitrogen compounds ; NO x ; NO3 ; N2O5 ; NO3 - ; NO2 - ; HNO3 ; HNO2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Four case studies are described, from a three-site field experiment in October/November 1991 using the Great Dun Fell flow-through reactor hill cap cloud in rural Northern England. Measurements of total odd-nitrogen nitrogen oxides (NO y ) made on either side of the hill, before and after the air flowed through the cloud, showed that 10 to 50% of the NO y , called NO z , was neither NO nor NO2. This NO z failed to exhibit a diurnal variation and was often higher after passage through cloud than before. No evidence of conversion of NO z to NO3 - in cloud was found. A simple box model of gas-phase chemistry in air before it reached the cloud, including scavenging of NO3 and N2O5 by aerosol of surface area proportional to the NO2 mixing ratio, shows that NO3 and N2O5 may build up in the boundary layer by night only if stable stratification insulates the air from emissions of NO. This may explain the lack of evidence for N2O5 forming NO3 - in cloud under well-mixed conditions in 1991, in contrast with observations under stably stratified conditions during previous experiments when evidence of N2O5 was found. Inside the cloud, some variations in the calculated total atmospheric loading of HNO2 and the cloud liquid water content were related to each other. Also, indications of conversion of NO x to NO z were found. To explain these observations, scavenging of NO x and HNO2 by cloud droplets and/or aqueous-phase oxidation of NO2 - by nitrate radicals are considered. When cloud acidity was being produced by aqueous-phase oxidation of NO x or SO2, NO3 - which had entered the cloud as aerosol particles was liberated as HNO3 vapour. When no aqueous-phase production of acidity was occurring, the reverse, conversion of scavenged HNO3 to particulate NO3 -, was observed.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 29 (1998), S. 299-314 
    ISSN: 1573-0662
    Keywords: rate constant ; temperaturedependence ; troposphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Accurate values for the rate and temperature dependence of the reaction NO + O3 → NO2 + O2 are important in the chemical modelling of photochemical processes in the atmosphere. Previous measurements have been made at low total pressures and/or with very large mixing ratios relative to those observed in the atmosphere. In this study the reaction rate has been measured using a novel approach under tropospheric conditions of temperature and pressure, and at tens of ppb (mixing ratios of 1 in 108) between 263 and 328 K. The resultant Arrhenius expression (k=Ae-Ea/RT) gives a larger activation energy (Ea/R=1670 ± 100) than the recommended literature value (Ea/R=1400 ± 200), and a larger pre-exponential factor (A=5.1 ± 1.6 × 10-12 cf. recommended A=2.0 × 10-12), but the second-order rate constant at 298 K (1.90 × 10-14 molecules cm-3 s-1 ± 10%) is similar to the recommended value. The results confirm a lack of pressure dependence of the reaction, but were made over too small a range in temperature to address the issue of curvature of the simple Arrhenius expression.
    Type of Medium: Electronic Resource
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