The Mechanism of Reactive NO3 Uptake on Dry NaX (X=Cl, Br)

A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO₃(g) + NaX(s) (NO₃-NaX)(s); (NO₃-NaX)(s) NaNO₃ + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO₃ for raw coating. The initial (t0) is higher than the observable steady-state _obs. At room temperature _obs is independent of [NO₃] at low [NO₃] = 3 × 10⁹ - 10¹¹ cm^-3, but it is inversely proportional to [NO₃] at concentrations higher than 10¹² cm^-3. At temperatures above 100 °C, _obs becomes independent of [NO₃] in a wider range of [NO₃]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to _obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO₃ concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.