Adsorption and heterogeneous reactions of ClONO₂ and N₂O₅ on/with NaCl aerosol

Abstract

The adsorption and heterogeneous reactions of ClONO2 and N2O5 on the NaCl (100) surface have been investigated by performing density functional theory (DFT) calculations.

SN2 Reactions of N2O5 with Ions in Water: Microscopic Mechanisms, Intermediates, and Products

“…It is known that if anions are present in water, the product branching fractions are changed. ,,,− One of the most studied halide substitution reactions is the reaction of N 2 O 5 with chloride-containing salty water, causing the formation of nitryl chloride (ClNO 2 ), a source of reactive chlorine radicals in the atmosphere. ,− , ClNO 2 is formed during the night and undergoes photolysis in the morning to produce halide radicals and nitrogen dioxide (NO 2 ). Despite the importance of this process, the mechanism of formation of ClNO 2 from the reaction between intact N 2 O 5 and Cl – is not completely understood.…”

Atmospheric Oxidation of Piperazine Initiated by ·Cl: Unexpected High Nitrosamine Yield

“…Chlorine radicals (·Cl) have a high oxidation ability toward volatile organic pollutants, with rate constants that are most often an order of magnitude larger than those of hydroxyl radicals (·OH). − ·Cl were historically considered to be produced primarily from heterogeneous reaction cycles involving sea salt, ,− and the concentration of ·Cl ([·Cl]) in the marine boundary layer is approximately 1–10% of [·OH]. − Therefore, the importance of ·Cl on the oxidation of tropospheric organic pollutants had been thought to be limited to the marine boundary layer. However, in the last seven years, a significant ·Cl source from ClNO 2 has been identified in midcontinental areas, such as North America, Central Europe, and Western Europe, − and very recently an even higher concentration of ClNO 2 was detected in the urban atmosphere of northern China, , suggesting ·Cl also play an important role in transforming atmospheric organics in continental areas.…”