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Atmospheric Chemistry of CH 2 OO: The Hydrolysis of CH 2 OO in Small Clusters of Sulfuric Acid.
- Source :
-
The journal of physical chemistry. A [J Phys Chem A] 2021 Apr 01; Vol. 125 (12), pp. 2642-2652. Date of Electronic Publication: 2021 Mar 23. - Publication Year :
- 2021
-
Abstract
- The hydrolysis of CH <subscript>2</subscript> OO is not only a dominant sink for the CH <subscript>2</subscript> OO intermediate in the atmosphere but also a key process in the formation of aerosols. Herein, the reaction mechanism and kinetics for the hydrolysis of CH <subscript>2</subscript> OO catalyzed by the precursors of atmospheric aerosols, including H <subscript>2</subscript> SO <subscript>4</subscript> , H <subscript>2</subscript> SO <subscript>4</subscript> ···H <subscript>2</subscript> O, and (H <subscript>2</subscript> SO <subscript>4</subscript> ) <subscript>2</subscript> , have been studied theoretically at the CCSD(T)-F12a/cc-pVDZ-F12//B3LYP/6-311+G(2 df ,2 pd ) level. The calculated results show that the three catalysts decrease the energy barrier by over 10.3 kcal·mol <superscript>-1</superscript> ; at the same time, the product formation of HOCH <subscript>2</subscript> OOH is more strongly bonded to the three catalysts than to the reactants CH <subscript>2</subscript> OO and H <subscript>2</subscript> O, revealing that small clusters of sulfuric acid promote the hydrolysis of CH <subscript>2</subscript> OO both kinetically and thermodynamically. Kinetic simulations show that the H <subscript>2</subscript> SO <subscript>4</subscript> -assisted reaction is more favorable than the H <subscript>2</subscript> SO <subscript>4</subscript> ···H <subscript>2</subscript> O- (the pseudo-first-order rate constant being 27.9-11.5 times larger) and (H <subscript>2</subscript> SO <subscript>4</subscript> ) <subscript>2</subscript> - (between 2.8 × 10 <superscript>4</superscript> and 3.4 × 10 <superscript>5</superscript> times larger) catalyzed reactions. Additionally, due to relatively lower concentration of H <subscript>2</subscript> SO <subscript>4</subscript> , the hydrolysis of CH <subscript>2</subscript> OO with H <subscript>2</subscript> SO <subscript>4</subscript> cannot compete with the CH <subscript>2</subscript> OO + H <subscript>2</subscript> O or (H <subscript>2</subscript> O) <subscript>2</subscript> reaction within the temperature range of 280-320 K, since its pseudo-first-order rate ratio is smaller by 4-7 or 6-8 orders of magnitude, respectively. However, the present results provide a good example of how small clusters of sulfuric acid catalyze the hydrolysis of an important atmospheric species.
Details
- Language :
- English
- ISSN :
- 1520-5215
- Volume :
- 125
- Issue :
- 12
- Database :
- MEDLINE
- Journal :
- The journal of physical chemistry. A
- Publication Type :
- Academic Journal
- Accession number :
- 33755485
- Full Text :
- https://doi.org/10.1021/acs.jpca.1c02006