TY - JOUR
T1 - Reacto-Diffusive Length of N2O5 in Aqueous Sulfate- and Chloride-Containing Aerosol Particles
AU - Gaston, Cassandra J.
AU - Thornton, Joel A.
N1 - Funding Information:
F. D. Lopez-Hilfiker is acknowledged for assistance with calibrating the CIMS for N2O5 and ClNO2. Funding for this work was provided by the National Science Foundation through award ECS-623046.
PY - 2016/2/25
Y1 - 2016/2/25
N2 - Heterogeneous reactions of dinitrogen pentoxide (N2O5) on aerosol particles impact air quality and climate, yet aspects of the relevant physical chemistry remain unresolved. One important consideration is the competing effects of diffusion and the rate of chemical reaction within the particle, which determines the length that N2O5 travels within a particle before reacting, referred to as the reacto-diffusive length (l). Large values of l imply a dependence of the reactive uptake efficiency of N2O5, i.e., γ(N2O5), on particle size. We present measurements of the size dependence of γ(N2O5) on aqueous sodium chloride, ammonium sulfate, and ammonium bisulfate particles. γ(N2O5) on ammonium sulfate and ammonium bisulfate particles ranged from 0.016 ± 0.005 to 0.036 ± 0.001 as the surface-area-weighted particle radius increased from 39 to 127 nm, resulting in an estimated l of 32 ± 6 nm. In contrast, γ(N2O5) on sodium chloride particles was independent of particle size, suggesting a near-surface reaction dominated the uptake of N2O5. Differences in the reactivity of the N2O5 intermediate, NO2+, with water and chloride can explain the observed dependencies. These results allow for parameterizations in atmospheric models to determine a more robust population mean value of γ(N2O5) that accounts for the distribution of particle sizes. (Chemical Equation Presented).
AB - Heterogeneous reactions of dinitrogen pentoxide (N2O5) on aerosol particles impact air quality and climate, yet aspects of the relevant physical chemistry remain unresolved. One important consideration is the competing effects of diffusion and the rate of chemical reaction within the particle, which determines the length that N2O5 travels within a particle before reacting, referred to as the reacto-diffusive length (l). Large values of l imply a dependence of the reactive uptake efficiency of N2O5, i.e., γ(N2O5), on particle size. We present measurements of the size dependence of γ(N2O5) on aqueous sodium chloride, ammonium sulfate, and ammonium bisulfate particles. γ(N2O5) on ammonium sulfate and ammonium bisulfate particles ranged from 0.016 ± 0.005 to 0.036 ± 0.001 as the surface-area-weighted particle radius increased from 39 to 127 nm, resulting in an estimated l of 32 ± 6 nm. In contrast, γ(N2O5) on sodium chloride particles was independent of particle size, suggesting a near-surface reaction dominated the uptake of N2O5. Differences in the reactivity of the N2O5 intermediate, NO2+, with water and chloride can explain the observed dependencies. These results allow for parameterizations in atmospheric models to determine a more robust population mean value of γ(N2O5) that accounts for the distribution of particle sizes. (Chemical Equation Presented).
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U2 - 10.1021/acs.jpca.5b11914
DO - 10.1021/acs.jpca.5b11914
M3 - Article
AN - SCOPUS:84959441140
VL - 120
SP - 1039
EP - 1045
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 7
ER -