Articles | Volume 25, issue 11
https://doi.org/10.5194/acp-25-5695-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-25-5695-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
11 Jun 2025
Research article |
| 11 Jun 2025
| 11 Jun 2025
Enhancing SO3 hydrolysis and nucleation: the role of formic sulfuric anhydride
Rui Wang
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, P. R. China
Rongrong Li
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, P. R. China
Shasha Chen
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, P. R. China
Ruxue Mu
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, P. R. China
Changming Zhang
Shaanxi Key Laboratory of Catalysis, School of Mechanical Engineering, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, P. R. China
Xiaohui Ma
CORRESPONDING AUTHOR
School of Environmental Engineering, Henan University of Technology, Zhengzhou, Henan 450001, P. R. China
Majid Khan
College of Chemistry, Fuzhou University, Fuzhou, Fujian 350116, P. R. China
Tianlei Zhang
CORRESPONDING AUTHOR
Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, P. R. China
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In the gaseous reaction, the activation energy for the hydrolysis of HNSO2 catalyzed by MSA was only 0.8 kcal mol−1. Atmospheric Cluster Dynamic Code kinetic simulations disclosed that sulfamic acid markedly enhances the assembly of a methanesulfonic acid–methylamine-based cluster. At the air–water interface, the NH2SO3− and H3O+ ion formation mechanism and the proton exchange mechanism were observed.
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In this work, NSA formation from SO3 + HNO3 was studied using quantum chemistry + ACDC. The reaction has a 3.61 kcal·mol-1 barrier and competes with SO3 sinks (HCOOH, C6H5COOH, NH3, H2O). NSA enhances interactions, lowers free energies, stabilizing SA–A clusters. ACDC shows SA–A nucleation up to ~10-3 cm-3 s-1 (278 .15K), ~5 orders above binary. NSA contribution increases with concentration and is stronger than HNO3.
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This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
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Benzoic sulfuric anhydride is a potential precursor to atmospheric new particle formation. We used calculations and kinetic modeling to investigate how it forms and influences sulfuric acid-amine particle formation. It forms readily in the gas phase and is a previously unrecognized sulfur-containing species that stabilizes molecular clusters more effectively than benzoic acid. Thus, it promotes particle formation in polluted cities and helps explain why these events occur so frequently.
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In the gaseous reaction, the activation energy for the hydrolysis of HNSO2 catalyzed by MSA was only 0.8 kcal mol−1. Atmospheric Cluster Dynamic Code kinetic simulations disclosed that sulfamic acid markedly enhances the assembly of a methanesulfonic acid–methylamine-based cluster. At the air–water interface, the NH2SO3− and H3O+ ion formation mechanism and the proton exchange mechanism were observed.
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The formation mechanisms of secondary organic aerosol and brown carbon from small α-carbonyls are still unclear. Thus, the mechanisms and kinetics of aqueous-phase reactions of glyoxal were investigated using quantum chemical and kinetic rate calculations. Several essential isomeric processes were identified, including protonation to yield diol/tetrol and carbenium ions as well as nucleophilic addition of carbenium ions to diol/tetrol and free methylamine/ammonia.
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Short summary
Gaseous results indicated that SO3 hydrolysis with formic sulfuric anhydride (FSA) has a Gibbs free energy barrier as low as 1.5 kcal mol-1 and can effectively compete with other SO3 hydrolysis. Interfacial BOMD (Born–Oppenheimer molecular dynamics) simulations illustrated that FSA-mediated SO3 hydrolysis at the gas–liquid interface occurs through a stepwise mechanism and can be completed within a few picoseconds. ACDC (Atmospheric Clusters Dynamics Code) kinetic simulations indicated that FSA significantly enhances cluster formation rates in the H2SO4–NH3 system.
Gaseous results indicated that SO3 hydrolysis with formic sulfuric anhydride (FSA) has a Gibbs...
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