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  • 1
    Publication Date: 2019-06-28
    Description: Fourier transform infrared (FTIR) spectroscopy has been used to study nitric-acid/ice films representative of type I polar stratospheric clouds (PSCs). These studies reveal that in addition to amorphous nitric acid/ice mixtures, there are three stable stoichiometric hydrates of nitric acid: nitric-acid monohydrate (NAM), dihydrate (NAD), and trihydrate (NAT). We also observe two distinct crystalline forms of the trihydrate, which we denote alpha- and beta-NAT. These two forms appear to differ in their concentration of crystalline defects, but not in their chemical composition. In addition to probing the composition of type I PSCs, we have also used FTIR spectroscopy to study the interaction of HCl with model PSC films. In this work we find that for HCl pressures in the range 10 exp -5 to 10 exp -7 Torr, HCl is taken up by ice at 155 K to form a thin layer of HCl.6H2O. At 193 K, the uptake of HCl by ice was consistent with less than or equal to monolayer coverage. Uptake of HCl by alpha and beta-NAT at 175 K was also consistent with less than or equal to monolayer coverage.
    Keywords: GEOPHYSICS
    Type: In: Optical methods in atmospheric chemistry; Proceedings of the Meeting, Berlin, Germany, June 22-24, 1992 (A93-51501 22-35); p. 48-58.
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  • 2
    Publication Date: 2019-07-12
    Keywords: GEOPHYSICS
    Type: Journal of Geophysical Research (ISSN 0148-0227); 97; D8 M
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  • 3
    Publication Date: 2019-07-13
    Description: Heterogeneous reactions involving hydrochloric acid adsorbed on the surfaces of polar stratospheric clouds (PSCs) are postulated to contribute to polar ozone loss. Using FTIR spectroscopy to probe the condensed phase, we have examined the interaction of HCl with ice and nitric acid trihydrate (NAT) films representative of types II and I PSCs, respectively. For HCl pressures in the range of 10 exp -7 to 10 exp -5 Torr, our FTIR studies show that a small amount of crystalline HCl-6H2O formed on or in ice at 155 K. However, for higher HCl pressures, we observed that the entire film of ice rapidly converted into an amorphous 4:1 H2O:HCl mixture. From HCl-uptake experiments with P(HCl) = 8 x 10 exp -7 Torr, we estimate roughly that the diffusion coefficient of HCl in ice is around 2 x 10 exp -12 sq cm/s at 158 K. For higher temperatures more closely approximating those found in the stratosphere, we were unable to detect bulk HCl uptake by ice. Indirect evidence suggests that HCl adsorption onto the surface of model PSC films inhibited the evaporation of both ice and NAT by 3-5 K.
    Keywords: GEOPHYSICS
    Type: Journal of Geophysical Research (ISSN 0148-0227); 98; D6; p. 10,563-10,571.
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  • 4
    Publication Date: 2019-07-13
    Description: Fourier transform infrared spectroscopy was used to examine the competitive growth of films representative of polar stratospheric clouds. These experiments show that either crystalline nitric acid trihydrate (beta-NAT) or amorphous films with H2O:HNO3 ratios close to 3:1 formed at temperatures 3-7 K warmer than the ice frost point under stratospheric pressure conditions. In addition, with higher HNO3 pressure, we observed nitric acid dihydrate (NAD) formation at temperatures warmer than ice formation. However, our experiments also show that NAD surfaces converted to beta-NAT upon exposure to stratospheric water pressures. Finally, we determined that the net uptake coefficient for HNO3 on beta-NAT is close to unity, whereas the net uptake coefficient for H2O is much less.
    Keywords: GEOPHYSICS
    Type: Geophysical Research Letters (ISSN 0094-8276); 19; 24; p. 2417-2420.
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  • 5
    Publication Date: 2019-07-12
    Description: Fourier-transform infrared surface studies are used to probe the microphysical properties of nitric acid trihydrate (NAT) and ice films representative of type I and II polar stratospheric clouds (PSC). Experiments indicate that, on initial exposure to 1.8 microtorr of HNO3, a layer of ice is quantitatively converted to NAT. However, conversion of ice to NAT does not proceed indefinitely, but rather the system reaches saturation. For longer exposures or higher HNO3 pressures, NAM becomes the dominant nitric acid containing species on the surface. Evaporation studies were performed to test the feasibility of a recent denitrification mechanism. The results indicate that ice coated with 0.20 micron of NAT evaporates at a temperature of about 4 C higher than uncoated ice.
    Keywords: GEOPHYSICS
    Type: Journal of Geophysical Research (ISSN 0148-0227); 95; 22423-22
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