Mechanistic insight into the competition between interfacial and bulk reactions in microdroplets through N 2 O 5 ammonolysis and hydrolysis.

Reactive uptake of dinitrogen pentaoxide (N ₂ O ₅ ) into aqueous aerosols is a major loss channel for NO _x in the troposphere; however, a quantitative understanding of the uptake mechanism is lacking. Herein, a computational chemistry strategy is developed employing high-level quantum chemical methods; the method offers detailed molecular insight into the hydrolysis and ammonolysis mechanisms of N ₂ O ₅ in microdroplets. Specifically, our calculations estimate the bulk and interfacial hydrolysis rates to be (2.3 ± 1.6) × 10 ^-3 and (6.3 ± 4.2) × 10 ^-7 ns ^-1 , respectively, and ammonolysis competes with hydrolysis at NH ₃ concentrations above 1.9 × 10 ^-4 mol L ^-1 . The slow interfacial hydrolysis rate suggests that interfacial processes have negligible effect on the hydrolysis of N ₂ O ₅ in liquid water. In contrast, N ₂ O ₅ ammonolysis in liquid water is dominated by interfacial processes due to the high interfacial ammonolysis rate. Our findings and strategy are applicable to high-chemical complexity microdroplets.
(© 2024. The Author(s).)