The heterogeneous formation of N2O in air containing NO2, O3 and NH3

Abstract

In a nighttime system and under relatively dry conditions (about 15 ppm H2O), the reaction mixture of NO2, O3, and NH3 in purified air turns out to result in the formation of nitrous oxide (N2O). The experiments were performed in a continuous stirred flow reactor, in the concentration region of 0.02–2 ppm. N2O is thought to arise through the heterogeneous reaction of gaseous N2O5 and absorbed NH3 at the wall of the reaction vessel % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9sq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9pue9Fve9% Ffc8meGabaqaciGacaGaaeqabaWaaeaaeaaakeaatCvAUfKttLeary% qr1ngBPrgaiuaacqWFOaakcqWFobGtcqWFibasdaWgaaWcbaGae83m% amdabeaakiab-LcaPmaaBaaaleaacqWFHbqyaeqaaOGaey4kaSIaai% ikaiab-5eaonaaBaaaleaacqWFYaGmaeqaaOGae83ta80aaSbaaSqa% aiab-vda1aqabaGccaGGPaWaaSbaaSqaaiaadEgaaeqaaOGaeyOKH4% Qae8Nta40aaSbaaSqaaiab-jdaYaqabaGccqWFpbWtcqGHRaWkcqWF% ibascqWFobGtcqWFpbWtdaWgaaWcbaGae83mamdabeaakiabgUcaRi% ab-HeainaaBaaaleaacqWFYaGmaeqaaOGae83ta8eaaa!59AC!\[(NH_3 )_a + (N_2 O_5 )_g \to N_2 O + HNO_3 + H_2 O\] In principle, there is competition between this reaction and that of adsorbed H2O with N2O5, resulting in the formation of HNO3. At high water concentrations (RH>75%), no formation of N2O was found. Although the rate constant of adsorbed NH3 with gaseous N2O5 is much larger than that of the reaction of adsorbed H2O with gaseous N2O5, the significance of the observed N2O formation for the outside atmosphere is thought to be dependent on the adsorption properties of H2O and NH3 on a surface. A number of NH3 and H2O adsorption measurements on several materials are discussed.