A potential source of tropospheric secondary organic aerosol precursors: The hydrolysis of N2O5 in water dimer and small clusters of sulfuric acid. (15th October 2022)

• Record Type: Journal Article
• Authors: Wen, Mingjie; Li, Rongrong; Zhang, Tianlei; Ding, Chao; Hu, Yue; Mu, Ruxue; Liang, Meng; Ou, Ting; Long, Bo
• Is Part Of: Atmospheric environment. Volume 287(2022)
• Publication Date: 2022-10-15
• Subjects: Air -- Pollution -- Periodicals; Air -- Pollution -- Meteorological aspects -- Periodicals; 551.51
• DOI: 10.1016/j.atmosenv.2022.119245
• Languages: English
• ISSNs: 1352-2310

Abstract

Abstract: The hydrolysis of dinitrogen pentoxide (N2 O5 ) is not only a dominant sink for N2 O5 under atmospheric conditions but also a critical route in the formation of acid rains and aerosol clusters. Herein, the hydrolysis of N2 O5 assisted by (H2 O)2, H2 SO4, H2 SO4 ⋯ H2 O, and (H2 SO4 )2 has been investigated theoretically. The calculations show that, as compared with catalysts of H2 O and NH3, the addition of (H2 O)2, H2 SO4, H2 SO4 ⋯ H2 O, and (H2 SO4 )2 in the hydrolysis of N2 O5 not only reduces another energy barrier of 8.7–18.2 kcal mol −1, but also plays a more crucial catalytic role in increasing the reaction rate by at least 2 orders of magnitude within the 213–300 K. Pseudo-first-order rate coefficient ( k t ′) show that (H2 SO4 )2 -assisted reaction is the favorable hydrolysis of N2 O5 assisted by small clusters of sulfuric acid (H2 SO4 in 10 8 molecules ⋅ cm −3 and H2 O in 100% RH) with its k t ′ respectively larger by 2–6 and 1–5 orders of magnitude. Moreover, (H2 O)2– assisted N2 O5 + H2 O reaction dominates over the reaction without and with (H2 SO4 )2, H2 O (100% RH) and NH3 (2900 ppbv) within the 280–300 K and 0 km altitude, whereas (H2 SO4 )2– assisted reaction can make an important contribution to the hydrolysis of N2 O5 under atmospheric conditions of 213–259 K and 5–15 km. This work helps one understand the process of HNO3 formation from the hydrolysis of N2 O5 promoted by water clusters and small clusters of sulfuric acid. Graphical abstract: Image 1 Highlights: The influence of water dimer and small clusters of H2 SO4 on the hydrolysis of N2 O5 were studied. Water dimer exerted a better catalytic role than other catalysts in hydrolysis of N2 O5 reaction. (H2 SO4 )2 will significantly promote the hydrolysis of N2 O5 at 213–259 K and 5–15 km.