Uptake of Gas-Phase Ammonia. 2. Uptake by Sulfuric Acid Surfaces

Swartz, E.; Qiu, Shi; Davidovits, P.; Jayne, J. T.; Worsnop, D. R.; Kolb, C. E.

doi:10.1021/jp991697h

Cited by 79 publications

(132 citation statements)

References 46 publications

Supporting

Mentioning

113

Contrasting

Order By: Relevance

“…The current uptake coefficients leading to NH neutralization of sulfuric acid particle (∼ 0.5-1; Swartz et al, 1999). These results suggest that under these conditions, the formation of NOC can compete with the neutralization of acidic particles, possibly due to kinetic limitations on the uptake of NH 3 caused by the coating of SOA as has been demonstrated previously (Liggio et al, 2011).…”

Section: Reaction Kineticssupporting

confidence: 66%

Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

Liu¹,

Liggio²,

Staebler³

et al. 2015

Atmos. Chem. Phys.

View full text Add to dashboard Cite

Abstract. As a class of brown carbon, organonitrogen compounds originating from the heterogeneous uptake of NH 3 by secondary organic aerosol (SOA) have received significant attention recently. In the current work, particulate organonitrogen formation during the ozonolysis of α-pinene and the OH oxidation of m-xylene in the presence of ammonia (34-125 ppb) was studied in a smog chamber equipped with a high resolution time-of-flight aerosol mass spectrometer and a quantum cascade laser instrument. A large diversity of nitrogen-containing organic (NOC) fragments was observed which were consistent with the reactions between ammonia and carbonyl-containing SOA. Ammonia uptake coefficients onto SOA which led to organonitrogen compounds were reported for the first time, and were in the range of ∼ 10 −3 -10 −2 , decreasing significantly to < 10 −5 after 6 h of reaction. At the end of experiments (∼ 6 h) the NOC mass contributed 8.9 ± 1.7 and 31.5 ± 4.4 wt % to the total α-pineneand m-xylene-derived SOA, respectively, and 4-15 wt % of the total nitrogen in the system. Uptake coefficients were also found to be positively correlated with particle acidity and negatively correlated with NH 3 concentration, indicating that heterogeneous reactions were responsible for the observed NOC mass, possibly limited by liquid phase diffusion. Under these conditions, the data also indicate that the formation of NOC can compete kinetically with inorganic acid neutralization. The formation of NOC in this study suggests that a significant portion of the ambient particle associated N may be derived from NH 3 heterogeneous reactions with SOA. NOC from such a mechanism may be an important and unaccounted for source of PM associated nitrogen. This mechanism may also contribute to the medium or long-range transport and wet/dry deposition of atmospheric nitrogen.

show abstract

Section: Reaction Kineticssupporting

confidence: 66%

Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

Liu¹,

Liggio²,

Staebler³

et al. 2015

Atmos. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…The applicability of β FS for trace gases in air (including species with higher molecular mass) has been confirmed by good agreement with experimental data (Li and Davis, 1996;Widmann and Davis, 1997;Seinfeld and Pandis, 1998;Swartz et al, 1999;Worsnop et al, 2001). By inserting β FS instead of β F in Eq.…”

Section: Gas Kinetic Fluxes and Uptake Coefficientssupporting

confidence: 56%

“…(15) and rearrangement using J net,Xi = F net,Xi /(d 2 p π) and Eq. (9), C g,Xi can be flexibly adapted to the approach of Fuchs and Sutugin (1971): (Li and Davis, 1996;Widmann and Davis, 1997;Seinfeld and Pandis, 1998;Swartz et al, 1999;Worsnop et al, 2001). More elaborate formalisms may be required for non-isothermal processes ), but several studies have shown that the formulation of Fuchs and Sutugin (1971) works well also under non-isothermal conditions (Kulmala and Vesala, 1991;Vesala et al, 1997;Kulmala and Wagner, 2001;Winkler et al, 2004).…”

Section: Gas Kinetic Fluxes and Uptake Coefficientsmentioning

confidence: 99%

Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 1: General equations, parameters, and terminology

2007

View full text Add to dashboard Cite

Abstract. Aerosols and clouds play central roles in atmospheric chemistry and physics, climate, air pollution, and public health. The mechanistic understanding and predictability of aerosol and cloud properties, interactions, transformations, and effects are, however, still very limited. This is due not only to the limited availability of measurement data, but also to the limited applicability and compatibility of model formalisms used for the analysis, interpretation, and description of heterogeneous and multiphase processes. To support the investigation and elucidation of atmospheric aerosol and cloud surface chemistry and gasparticle interactions, we present a comprehensive kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters. It enables a detailed description of mass transport and chemical reactions at the gas-particle interface, and it allows linking aerosol and cloud surface processes with gas phase and particle bulk processes in systems with multiple chemical components and competing physicochemical processes.The key elements and essential aspects of the presented framework are: a simple and descriptive double-layer surface model (sorption layer and quasi-static layer); straightforward flux-based mass balance and rate equations; clear separation of mass transport and chemical reactions; well-defined and consistent rate parameters (uptake and accommodation coefficients, reaction and transport rate coefficients); clear distinction between gas phase, gas-surface, and surfacebulk transport (gas phase diffusion, surface and bulk accommodation); clear distinction between gas-surface, surface layer, and surface-bulk reactions (Langmuir-Hinshelwood and Eley-Rideal mechanisms); mechanistic description of The outlined double-layer surface concept and formalisms represent a minimum of model complexity required for a consistent description of the non-linear concentration and time dependences observed in experimental studies of atmospheric multiphase processes (competitive co-adsorption and surface saturation effects, etc.). Exemplary practical applications and model calculations illustrating the relevance of the above aspects are presented in a companion paper (Ammann and Pöschl, 2007).We expect that the presented model framework will serve as a useful tool and basis for experimental and theoretical studies investigating and describing atmospheric aerosol and cloud surface chemistry and gas-particle interactions. It shall help to end the "Babylonian confusion" that seems to inhibit scientific progress in the understanding of heterogeneous chemical reactions and other multiphase processes in aerosols and clouds. In particular, it shall support the planning and design of laboratory experiments for the elucidation and determination of fundamental kinetic parameters; the establishment, evaluation, and quality assurance of comprehensive and self-consistent collections of rate parameters; and the development of detailed master mechanisms for process mo...

show abstract

“…It should be noted, however, that ambient ammonia concentrations tend to be an order of magnitude greater than amine concentrations (Murphy et al, 2007), and the uptake coefficient of ammonia by H 2 SO 4 , approximately 1 (Liggio et al, 2011;Shi et al, 1999;Swartz et al, 1999), is also one or two orders of magnitude greater than that of amine. Conversely, the dissociation constants of aminium nitrate are greater than or equal to that of NH 4 NO 3 (Murphy et al, 2007).…”

Section: Introductionmentioning

confidence: 94%

Differences in the reactivity of ammonium salts with methylamine

et al. 2012

View full text Add to dashboard Cite

Abstract. The heterogeneous uptake of methylamine (MA) onto (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 NO 3 and NH 4 Cl was investigated using a Knudsen cell reactor coupled to a quadrupole mass spectrometer, in situ Raman spectrometer and theoretical calculations. Exchange reactions were observed between MA and NH 4 NO 3 , (NH 4 ) 2 SO 4 , and NH 4 Cl were observed at 298 K. Simple acid-base reaction for MA was found taking place on NH 4 HSO 4 . CH 3 NH 3 NO 3 and CH 3 NH 3 Cl are not stable at low pressure and have higher dissociation vapor pressure than methylammonium sulfate. The observed uptake coefficients of MA on (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 NO 3 and NH 4 Cl at 298 K were measured to be 6.30±1.03×10 −3 , 1.78±0.36×10 −2 , 8.79±1.99×10 −3 and 2.29±0.28×10 −3 , respectively. A linear free energy relationship was found for the heterogeneous reactions between MA and NH 4 Cl, (NH 4 ) 2 SO 4 and NH 4 NO 3 . Namely, the natural logarithm of uptake coefficients of MA on these ammonium salts is linearly related to the electrostatic potential of the H atom in the NH + 4 group.

show abstract

Uptake of Gas-Phase Ammonia. 2. Uptake by Sulfuric Acid Surfaces

Cited by 79 publications

References 46 publications

Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions – Part 1: General equations, parameters, and terminology

Differences in the reactivity of ammonium salts with methylamine

Contact Info

Product

Resources

About