Photochemistry of nitrous acid (HONO) and nitrous acidium ion (H2ONO) in aqueous solution and ice

Environ Sci Technol. 2009 Feb 15;43(4):1108-14. doi: 10.1021/es802579a.

Abstract

We have examined the photochemistries of two N(III) species, nitrous acid (HONO) and nitrous acidium ion (H2ONO+), 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 H2ONO+ at 274 K. The temperature dependent expressions for the *OH (and NO) quantum yields are In(phi(HONO --> *OH) = (7.14 +/- 0.57) - (2430 +/- 160)/T and In(phi(H2ONO+ --> *OH) = (3.16 +/- 0.67) - (1890 +/- 180)/T. The temperature dependence for H2ONO+ 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 H2ONO+ are independent of wavelength, in contrast to NO2-. On the basis of the pH dependence of N(III) photolysis, our results are consistent with recently reported pKa values of 1.7 for H2ONO+ and 2.8 for HONO. Using our results in a kinetic model of nitrogen chemistry illustrates that the fluxes of HONO and NO(x) 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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Absorption / radiation effects
  • Anions / chemistry*
  • Environment
  • Hydrogen-Ion Concentration / radiation effects
  • Hydroxyl Radical / chemistry
  • Ice*
  • Ions
  • Least-Squares Analysis
  • Nitrogen / chemistry
  • Nitrous Acid / chemistry*
  • Photochemical Processes*
  • Photolysis / radiation effects
  • Photons
  • Solutions
  • Sunlight
  • Temperature
  • Water / chemistry*

Substances

  • Anions
  • Ice
  • Ions
  • Solutions
  • Water
  • Hydroxyl Radical
  • Nitrogen
  • Nitrous Acid