Thermodynamic Model of the System H+−NH4+−SO42-−NO3-−H2O at Tropospheric Temperatures

Clegg, Simon L.; Brimblecombe, Peter; Wexler, Anthony S.

doi:10.1021/jp973042r

Cited by 776 publications

(783 citation statements)

References 65 publications

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“…Deviations are typically <0.02 in osmotic coefficient for the (NH 4 ) 2 SO 4 , NaNO 3 , and NaCl systems, comparable to previous measurements (see, for example, the comparisons of predictions and measurements of osmotic coefficients in the work by Clegg et al 47 ). Larger discrepancies are observed for Na 2 SO 4 at intermediate concentrations and these have already been discussed above.…”

Section: The Journal Of Physical Chemistry Asupporting

confidence: 83%

“…To do this, the thermodynamic Extended Aerosol Inorganics Model (E-AIM) 5,6,47 (http://www.aim.env.uea.ac.uk/) is used to calculate how water activity and density change with the solution composition during evaporation and to predict the equilibrated radius of the droplet after water evaporation has ended at a given RH. For the relationship between water activity and NaCl concentration, the model is based upon the critical review of Archer, 48 and electrodynamic balance measurements of several authors (see Table 1 of Clegg et al 49 ).…”

Section: Aerosol Hygroscopic Growth From Comparativementioning

confidence: 99%

“…4 Rigorous thermodynamic models for calculating the hygroscopic response of mixed component aerosol have been developed on the basis of bulk phase and aerosol phase measurements of the equilibrium response of binary solutions of a single solute and water. 5,6 When combined with treatments of solution density and surface tension, accurate predictions of the variation in equilibrium particle size with relative humidity are possible. 7,8 To represent the equilibrium properties of solutions containing the myriad of potential organic compounds found in the atmosphere, it is often necessary to resort to functional group activity models that require consideration of the interactions between electrolytes and organic species.…”

Section: Introductionmentioning

confidence: 99%

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Accurate Measurements of Aerosol Hygroscopic Growth over a Wide Range in Relative Humidity

et al. 2016

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Using a comparative evaporation kinetics approach, we describe a new and accurate method for determining the equilibrium hygroscopic growth of aerosol droplets. The time-evolving size of an aqueous droplet, as it evaporates to a steady size and composition that is in equilibrium with the gas phase relative humidity, is used to determine the time-dependent mass flux of water, yielding information on the vapor pressure of water above the droplet surface at every instant in time. Accurate characterization of the gas phase relative humidity is provided from a control measurement of the evaporation profile of a droplet of know equilibrium properties, either a pure water droplet or a sodium chloride droplet. In combination, and by comparison with simulations that account for both the heat and mass transport governing the droplet evaporation kinetics, these measurements allow accurate retrieval of the equilibrium properties of the solution droplet (i.e., the variations with water activity in the mass fraction of solute, diameter growth factor, osmotic coefficient or number of water molecules per solute molecule). Hygroscopicity measurements can be made over a wide range in water activity (from >0.99 to, in principle, <0.05) on time scales of <10 s for droplets containing involatile or volatile solutes. The approach is benchmarked for binary and ternary inorganic solution aerosols with typical uncertainties in water activity of <±0.2% at water activities >0.9 and ∼±1% below 80% RH, and maximum uncertainties in diameter growth factor of ±0.7%. For all of the inorganic systems examined, the time-dependent data are consistent with large values of the mass accommodation (or evaporation) coefficient (>0.1).

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Section: The Journal Of Physical Chemistry Asupporting

confidence: 83%

Section: Aerosol Hygroscopic Growth From Comparativementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Accurate Measurements of Aerosol Hygroscopic Growth over a Wide Range in Relative Humidity

et al. 2016

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“…This interaction may also be important for MVK and the carbonyls reported previously, while the lack of an interaction for MACR may be related to the fact that it does not enolize. Also shown in Figure 3 are the effective Henry's law coefficients for H 2 O, normalized to the pure water value, obtained by applying eq 10 using the water content and the H 2 O vapor pressures of the acids, 34,35 at 298 and 250 K. The increase in this quantity occurs at similar acidities as those for the H enhanced for many of the organic compounds. The similarity of the tendencies indicates the increase in H A with acidity could be related to a solvation effect by HSO 4 -and/or another constituent of the solution.…”

Section: Discussionmentioning

confidence: 99%

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

et al. 2006

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To investigate the link between molecular structure, reactivity, and partitioning of oxygenated organic compounds in acidic aerosols, the uptake of three compounds found in the atmosphere, methyl vinyl ketone (MVK), methacrolein (MACR), and 2-methyl-3-butene-2-ol (MBO), by sulfuric acid solutions has been measured using a rotated wetted-wall reactor (RWW) coupled to a chemical ionization mass spectrometer (CIMS). MVK was found to partition reversibly into 20-75 wt % H 2 SO 4 solutions, and we report Henry's law coefficients between 20 and 7000 M atm -1 over this range. A chemical reaction for MVK was likely responsible for the uptake observed for 80-96 wt % H 2 SO 4 solutions. We derive an upper limit to the aldol self-reaction rate coefficient for MVK in 80 wt % solution of ∼3 M -1 s -1 . MACR partitioned reversibly over most of the acidity range, and in contrast to that for MVK, the Henry's law coefficient was relatively independent of H 2 SO 4 content. These differences indicate that the increase of the coefficient with acidity is likely due to the ability of the carbonyl molecule to form an enol. These results indicate that aldol condensation can be facile in concentrated sulfuric acid solutions, but it should be negligibly slow in dilute acid solutions such as tropospheric aerosols. MBO uptake could be explained by a Henry's law coefficient that decreases slightly as acid content varies from 20 to 55 wt % H 2 SO 4 ; we also measured the value in water, 70 M atm -1 at 298 K. A steady-state uptake of MBO was observed onto 40-80 wt % H 2 SO 4 solutions, a reaction product was observed, and the reaction was tentatively identified as Pinacol rearrangement. Similar rearrangements could be at the origin of some substituted oxygenated species found in atmospheric aerosols.

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“…The pH and liquid water content (LWC) of the aerosol phase were calculated using the Extended Aerosol Inorganics Model (E-AIM model II, http://www.aim.env.uea.ac.uk/aim/aim.php) 53,54 constrained by measurements of temperature, relative humidity, particle phase nitrate, sulfate, and ammonium. All solid formation was suppressed in the model and no organic compounds were included.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Observational Insights into Aerosol Formation from Isoprene

Worton

Surratt

LaFranchi

et al. 2013

Environ. Sci. Technol.

120

161

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Thermodynamic Model of the System H⁺−NH₄⁺−SO₄^2-−NO₃^-−H₂O at Tropospheric Temperatures

Cited by 776 publications

References 65 publications

Accurate Measurements of Aerosol Hygroscopic Growth over a Wide Range in Relative Humidity

Accurate Measurements of Aerosol Hygroscopic Growth over a Wide Range in Relative Humidity

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

Observational Insights into Aerosol Formation from Isoprene

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