Heterogeneous Reactions of N2O5 with Nitrate- and Chloride-Containing Solutions: Isotopic Evidence for the Nitration of N2O5

The nitrate (NO3 –) ion has been shown to suppress the reactive uptake of dinitrogen pentoxide (N2O5) to aqueous aerosol, yet a molecular mechanism that explains this effect remains elusive. To explore how N2O5 and NO3 – interact in solution, we use isotopically labeled 15NO3 – in the presence of Cl– to mark 14,14N2O5 that react with 15NO3 – by detecting the nitration and chlorination products 14,15N2O5, 15,15N2O5, Cl14NO2, and Cl15NO2. At three Na15NO3 concentrations (0.47, 1.35, and 3.7 M), both Cl14NO2 and Cl15NO2 products are measured as the NaCl concentration increases from 0 to 3.0 M, confirming that N2O5 can reactively exchange with NO3 – prior to chlorination. Using a kinetic multilayer model to compare chlorination and nitration (nitrate exchange) of N2O5, the rate constant ratio k Cl– /k NO3 – is determined to be between 2 and 6 for the three 15NO3 – concentrations. Model results suggest that the initial adsorption of a 14,14N2O5 molecule produces the majority of Cl15NO2 by exchange with 15NO3 – before reacting with Cl–, rather than occurring through multiple absorption and evaporation events involving 14,15N2O5 or 15,15N2O5. The ratio of nitrate exchange to hydrolysis, k NO3 – /k H2O, is inferred to be between 70 and 230, which overestimates nitrate suppression in 6 M NaNO3 by 10-fold when using previous parametrizations of N2O5 uptake based on an SN1 NO2 + mechanism. We propose an alternate SN2 mechanism involving N2O5 activation and deactivation that fits both isotope and uptake data.

• Publication year

  2025

• Venue

  Journal of Physical Chemistry A

• Publication date

  2025-11-10

• Fields of study

  Medicine, Chemistry, Environmental Science

• Identifiers
  DOI 10.1021/acs.jpca.5c06048PMID 41211660PMCID 12641490
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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