Leu, Ming-Taun and Timonen, Raimo S. and Keyser, Leon F. and Yung, Yuk L. (1995) Heterogeneous Reactions of HNO_3(g) + NaCl(s) → HCl(g) + NaNO_3(s) and N_2O_5(g) + NaCl(s) → ClNO_2(g) + NaNO_3(s). Journal of Physical Chemistry, 99 (35). pp. 13203-13212. ISSN 0022-3654. doi:10.1021/j100035a026. https://resolver.caltech.edu/CaltechAUTHORS:20140819-110325742
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Abstract
The heterogeneous reactions of HNO_3(g) + NaCl(s) → HCl(g) + NaNO_3(s) (eq 1) and N_2O_5(g) + NaCl(s) → ClNO_2(g) + NaNO_3(s) (eq 2) were investigated over the temperature range 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. Either a chemical ionization mass spectrometer (CIMS) or an electron-impact ionization mass spectrometer (EIMS) was used to provide suitable detection sensitivity and selectivity. In order to mimic atmospheric conditions, partial pressures of HNO_3 and N_2O_5 in the range 6 x 10^(-8) ~ 2 x 10^(-6) Torr were used. Granule sizes and surface roughness of the solid NaCl substrates were determined by using a scanning electron microscope. For dry NaCl substrates, decay rates of HNO_3 were used to obtain y(1) = 0.013 ± 0.004 (lo) at 296 K and >0.008 at 223 K, respectively. The error quoted is the statistical error. After all corrections were made, he overall error, including systematic error, was estimated to be about a factor of 2. HC1 was found to be the sole gas-phase product of reaction 1. The mechanism changed from heterogeneous reaction to predominantly physical adsorption when the reactor was cooled from 296 to 223 K. For reaction 2 using dry salts, y(2) was found to be less than 1.0 x 10^(-4) at both 223 and 296 K. The gas-phase reaction product was identified as ClNO_2 in previous studies using an infrared spectrometer. An enhancement in reaction probability was observed if water was not completely removed from salt surfaces, probably due to the reaction of N_2O_5(g) + H_2O(s) → 2HNO_3(g). Our results are compared with previous literature values obtained using different experimental techniques and conditions. The implications of the present results for the enhancement of the hydrogen chloride column density in the lower stratosphere after the El Chichon volcanic eruption and for the chemistry of HCl and HNO_3 in the marine troposphere are discussed.
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| Additional Information: | © 1995 American Chemical Society. Received: February 9, 1995; In Final Form: June 29, 1995. Publication Date: August 1995. The research described in this article was performed at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration. Y.L.Y. acknowledges support of NASA Grant NAGW 2204 to the California Institute of Technology. The authors are grateful to Veronica Bierbaum and Carleton Howard for helpful discussion on the development of CI mass spectrometry, Renyi Zhang for the design of the data acquisition system, and Greg Huey and Michel Rossi for sending preprints. | |||||||||
| Group: | UNSPECIFIED, Division of Geological and Planetary Sciences | |||||||||
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| Issue or Number: | 35 | |||||||||
| DOI: | 10.1021/j100035a026 | |||||||||
| Record Number: | CaltechAUTHORS:20140819-110325742 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20140819-110325742 | |||||||||
| Official Citation: | Heterogeneous Reactions of HNO3(g) + NaCl(s) .fwdarw. HCl(g) + NaNO3(s) and N2O5(g) + NaCl(s) .fwdarw. ClNO2(g) + NaNO3(s) Ming-Taun Leu, Raimo S. Timonen, Leon F. Keyser, and Yuk L. Yung The Journal of Physical Chemistry 1995 99 (35), 13203-13212 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 48683 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 19 Aug 2014 18:27 | |||||||||
| Last Modified: | 10 Nov 2021 18:34 |
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