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  • 1
    Publication Date: 2011-08-23
    Description: The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda 〉 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda 〉 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda 〉 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda 〉 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda 〉 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.
    Keywords: Inorganic and Physical Chemistry
    Type: Journal of Physical Chemistry (ISSN 0022-3654); Volume 100; No. 20; 10165-10178
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  • 2
    Publication Date: 2019-07-13
    Description: The uptake of peroxynitric acid (PNA), HO2NO2 or HNO4, on solid H2O ice at 193 K (-80 C) was studied using a fast flow-mass spectrometric technique. An uptake coefficient of 0.15 +/- 0.10 was measured, where the quoted uncertainty denotes 2 standard deviations. The uptake process did not result in the production of gas phase products. The composition of the condensed phase was investigated using programmed heating (3 K/min) of the substrate coupled with mass spectrometric detection of desorbed species. Significant quantities of HNO, and HNO3 desorbed from the substrates at temperatures above 225 K and 246 K, respectively. The desorbed HNO3, which was less than 9% of the desorbed HNO, and remained unchanged upon incubation of the substrate, was likely due to impurities in the HNO4 samples rather than reaction of HNO, on the substrate. The onset temperatures for HNO4 desorption increased with increasing H2O to HNO4 ratios, indicating that HNO4, like HNO3, tends to be hydrated in the presence of water. These observations suggest possible mechanisms for removal of HNO4 or repartitioning of total odd nitrogen species in the Earth's upper troposphere and stratosphere.
    Keywords: Inorganic and Physical Chemistry
    Type: Paper-96JD00065 , Journal of Geophysical Research (ISSN 0148-0227); 101; D3; 6795-6802
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  • 3
    Publication Date: 2019-08-17
    Description: Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations.
    Keywords: Inorganic and Physical Chemistry
    Type: NASA-CR-203214 , NAS 1.26:203214 , The Journal of Physical Chemistry (ISSN 0022-3654); 99; 8162-8169
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