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  • H 2 SO 4 and particle production in a photolytic flow reactor: chemical modeling, cluster thermodynamics and contamination issues
Title: H 2 SO 4 and particle production in a photolytic flow reactor: chemical modeling, cluster thermodynamics and contamination issues
Abstract. Size distributions of particles formed from sulfuric acid(H2SO4) and water vapor in a photolytic flow reactor (PhoFR) weremeasured with a nanoparticle mobility sizing system. Experiments with addedammonia and dimethylamine were also performed. H2SO4(g) wassynthesized from HONO, sulfur dioxide and water vapor, initiating OHoxidation by HONO photolysis. Experiments were performed at 296 K over arange of sulfuric acid production levels and for 16 % to 82 % relativehumidity. Measured distributions generally had a large-particle mode thatwas roughly lognormal; mean diameters ranged from 3 to 12 nm and widths(lnσ) were ∼0.3. Particle formation conditions werestable over many months. Addition of single-digit pmol mol−1 mixing ratios ofdimethylamine led to very large increases in particle number density.Particles produced with ammonia, even at 2000 pmol mol−1, showed that NH3is a much less effective nucleator than dimethylamine. A two-dimensionalsimulation of particle formation in PhoFR is also presented that starts withgas-phase photolytic production of H2SO4, followed by kineticformation of molecular clusters and their decomposition, which is determined by theirthermodynamics. Comparisons with model predictions of the experimentalresult's dependency on HONO and water vapor concentrations yieldphenomenological cluster thermodynamics and help delineate the effects ofpotential contaminants. The added-base simulations and experimental resultsprovide support for previously published dimethylamine–H2SO4cluster thermodynamics and provide a phenomenological set ofammonia–sulfuric acid thermodynamics.  more » « less
Award ID(s):
1761638
NSF-PAR ID:
10143283
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Atmospheric Chemistry and Physics
Volume:
19
Issue:
14
ISSN:
1680-7324
Page Range / eLocation ID:
8999 to 9015
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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