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Photochemical Production and Release of Gaseous NO_2 from Nitrate-Doped Water Ice

Boxe, C. S. and Colussi, A. J. and Hoffmann, M. R. and Murphy, J. G. and Wooldridge, P. J. and Bertram, T. H. and Cohen, R. C. (2005) Photochemical Production and Release of Gaseous NO_2 from Nitrate-Doped Water Ice. Journal of Physical Chemistry A, 109 (38). pp. 8520-8525. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154755438

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Abstract

Temperature-programmed NO_2 emissions from frozen aqueous NaNO_3 solutions irradiated at 313 nm were monitored as function of nitrate concentration and heating rate, H, above −30 °C. Emissions increase nonmonotonically with temperature, displaying transitions suggestive of underlying metamorphic transformations. Thus, NO_2 emissions surge at ca. −8 °C in frozen [NO_3^-] > 200 μM samples warmed at H = 0.70 °C min^(-1) under continuous irradiation, and also in the dark from samples that had been photolyzed at −30 °C. The amounts of NO_2 released in individual thermograms, Σ_N, increase less than linearly with [NO_3^-] or the duration of experiments, revealing the significant loss of photogenerated NO_2. The actual Σ_N ∝ [NO_3^-]^(1/2) dependence (at constant H) is consistent with NO_2 hydrolysis:  2NO_2 + H_2O → NO_3^- + NO_2^- + 2H^+, overtaking NO_2 desorption, even below the eutectic point (−18 °C for aqueous NaNO_3). The increasingly larger NO2 losses detected in longer experiments (at constant [NO_3^-]) are ascribed to secondary photolysis of trapped NO_2. The relevance of present results to the interpretation of polar NO_2 measurements is briefly analyzed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp0518815DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp0518815PublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Hoffmann, M. R.0000-0001-6495-1946
Bertram, T. H.0000-0002-3026-7588
Cohen, R. C.0000-0001-6617-7691
Additional Information:© 2005 American Chemical Society. Received: April 11, 2005; In Final Form: July 7, 2005. C.S.B. acknowledges support from the Betty and Gordon Moore Foundation. This work was financed by NSF grant ATM-0228140.
Funders:
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
NSFATM-0228140
Issue or Number:38
Record Number:CaltechAUTHORS:20150623-154755438
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150623-154755438
Official Citation:Photochemical Production and Release of Gaseous NO2 from Nitrate-Doped Water Ice C. S. Boxe, A. J. Colussi, M. R. Hoffmann, J. G. Murphy, P. J. Wooldridge, T. H. Bertram, and R. C. Cohen The Journal of Physical Chemistry A 2005 109 (38), 8520-8525 DOI: 10.1021/jp0518815
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58475
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:28 Jul 2015 21:28
Last Modified:09 Mar 2020 13:18

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