The Heterogeneous Reaction of NO₂ with NH₄Cl: A Molecular Diffusion Tube Study

ISSN： 0167-7764

Source： Journal of Atmospheric Chemistry, Vol.50, Iss.2, 2005-02, pp. : 171-194

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Abstract

The heterogeneous interaction of nitrogen dioxide with ammonium chloride was investigated in a molecular diffusion tube experiment at 295–335 K and interpreted using Monte Carlo trajectory calculations. The surface residence time (τ_surf) of NO₂ on NH₄Cl is equal to 15 μs at 295 K, increases with temperature up to 323 K (τ_surf = 45 μs) and probably decreases beyond 323 K. The same experiment also yields uptake coefficients, γ, which are derived from the absolute number of surviving molecules effusing out of the diffusion tube. The rate of uptake of NO₂ on NH₄Cl followed a rate law first order in [NO₂] and the uptake coefficient γ is equal to 7 × 10⁻⁵ at 295 K, increases with temperature up to 323 K (γ = 2.1 × 10⁻⁴) and probably decreases beyond 323 K. Nitrous acid, water and nitrogen were detected as products. From these products, it is concluded that the reaction of NO₂ with NH₄Cl is a reverse disproportionation reaction where two moles of NO₂ result in ammonium nitrite, NH₄NO₂, as an intermediate, and nitryl chloride, NO₂Cl. NH₄NO₂ decomposes in two pathways, one to nitrous acid, HONO and NH₃, the other to nitrogen and water. The branching ratio for the production of HONO + NH₃ to that of N₂ + H₂O is approximately 20 at 298 K and increases with increasing temperature.