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Photochemistry of nitrous acid (HONO) and nitrous acidium ion (H ONO ) in aqueous solution and ice

Environmental Science and Technology, ISSN: 0013-936X, Vol: 43, Issue: 4, Page: 1108-1114
2009
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We have examined the photochemistries of two N(III) species, nitrous acid (HONO) and nitrous acidium ion (H ONO ), in solution and ice. Although the light absorption spectra for these two species are very similar, their photochemical efficiencies are quite different: the OH (and NO) quantum yield for HONO is approximately 8 times greater than that of H ONO at 274 K. The temperature dependent expressions for the ̇OH (and NO) quantum yields are In(OΦ(HONO → OH) = (7.14 ± 0.57) - (2430 ± 160)/Tand ln(Φ(H ONO → OH) = (3.16 ± 0.67) - (1890 ± 180)/T. The temperature dependence for H ONO includes both solution and ice data (255-283 K), suggesting that its ice photochemistry is occurring in a quasi-liquid environment The quantum yields for HONO and H ONO are independent of wavelength, in contrast to NO . On the basis of the pH dependence of N(III) photolysis, our results are consistent with recently reported pK values of 1.7 for H ONO and 2.8 for HONO. Using our results in a kinetic model of nitrogen chemistry illustrates that the fluxes of HONO and NO from sunlit snow can be explained by nitrate photolysis and are pH dependent because of a competition between HONO evaporation and N(III) reactions on ice grains. © 2009 American Chemical Society.

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