Henry's law constants of polyols

Compernolle, Steven; Müller, J.-F.

doi:10.5194/acp-14-12815-2014

Cited by 15 publications

(12 citation statements)

References 84 publications

(211 reference statements)

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“…For highly functionalized species GECKO‐A predicts large H values up to 10 16 M/atm. Such high values (>10 12 M/atm) have recently been derived for polyols (compounds with two or more hydroxyl groups) using a different methodology from the one used in this study [ Compernolle and Müller , ]. Uncertainties associated with the GROMHE estimates in that range of values are expected to be significant, because the extrapolation is performed beyond experimentally measured values (typically up to 10 9 M/atm for oxalic acid [ Raventos‐Duran et al ., ]).…”

Section: Resultsmentioning

confidence: 99%

Volatility dependence of Henry's law constants of condensable organics: Application to estimate depositional loss of secondary organic aerosols

Hodzic

Aumont

Knote

et al. 2014

Geophysical Research Letters

128

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The water solubility of oxidation intermediates of volatile organic compounds that can condense to form secondary organic aerosol (SOA) is largely unconstrained in current chemistry-climate models. We apply the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere to calculate Henry's law constants for these intermediate species. Results show a strong negative correlation between Henry's law constants and saturation vapor pressures. Details depend on precursor species, extent of photochemical processing, and NO x levels. Henry's law constants as a function of volatility are made available over a wide range of vapor pressures for use in 3-D models. In an application using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) over the U.S. in summer, we find that dry (and wet) deposition of condensable organic vapors leads to major reductions in SOA, decreasing surface concentrations by~50% (10%) for biogenic and 40% (6%) for short chain anthropogenic precursors under the considered volatility conditions.

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Section: Resultsmentioning

confidence: 99%

Volatility dependence of Henry's law constants of condensable organics: Application to estimate depositional loss of secondary organic aerosols

Hodzic

Aumont

Knote

et al. 2014

Geophysical Research Letters

128

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“…Only very few experimental determinations of mass accommodation coefficients exist in the literature (see, e.g. the most recent IUPAC recommendation by Ammann et al, 2013; or the compilations by Davidovits et al, 2006Davidovits et al, , 2011. Therefore, it is impossible to derive advanced estimation methods for this parameter.…”

Section: Uptake Parametersmentioning

confidence: 99%

Development of a protocol for the auto-generation of explicit aqueous-phase oxidation schemes of organic compounds

et al. 2019

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Abstract. This paper presents a new CAPRAM–GECKO-A protocol for mechanism auto-generation of aqueous-phase organic processes. For the development, kinetic data in the literature were reviewed and a database with 464 aqueous-phase reactions of the hydroxyl radical with organic compounds and 130 nitrate radical reactions with organic compounds has been compiled and evaluated. Five different methods to predict aqueous-phase rate constants have been evaluated with the help of the kinetics database: gas–aqueous phase correlations, homologous series of various compound classes, radical reactivity comparisons, Evans–Polanyi-type correlations, and structure–activity relationships (SARs). The quality of these prediction methods was tested as well as their suitability for automated mechanism construction. Based on this evaluation, SARs form the basis of the new CAPRAM–GECKO-A protocol. Evans–Polanyi-type correlations have been advanced to consider all available H atoms in a molecule besides the H atoms with only the weakest bond dissociation enthalpies (BDEs). The improved Evans–Polanyi-type correlations are used to predict rate constants for aqueous-phase NO3 and organic compounds reactions. Extensive tests have been performed on essential parameters and on highly uncertain parameters with limited experimental data. These sensitivity studies led to further improvements in the new CAPRAM–GECKO-A protocol but also showed current limitations. Biggest uncertainties were observed in uptake processes and the estimation of Henry's law coefficients as well as radical chemistry, in particular the degradation of alkoxy radicals. Previous estimation methods showed several deficits, which impacted particle growth. For further evaluation, a 1,3,5-trimethylbenzene oxidation experiment has been performed in the aerosol chamber “Leipziger Aerosolkammer” (LEAK) at high relative humidity conditions and compared to a multiphase mechanism using the Master Chemical Mechanism (MCMv3.2) in the gas phase and using a methylglyoxal oxidation scheme of about 600 reactions generated with the new CAPRAM–GECKO-A protocol in the aqueous phase. While it was difficult to evaluate single particle constituents due to concentrations close to the detection limits of the instruments applied, the model studies showed the importance of aqueous-phase chemistry in respect to secondary organic aerosol (SOA) formation and particle growth. The new protocol forms the basis for further CAPRAM mechanism development towards a new version 4.0. Moreover, it can be used as a supplementary tool for aerosol chambers to design and analyse experiments of chemical complexity and help to understand them on a molecular level.

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“…The value of Δ soln H/R was chosen to approximate the range of values reported for multifunctional organics in Sander [] which go from ~4000 to ~9000 K. We ran the model for different values of the temperature dependence but did not find any differences for these conditions. This parameterization is consistent with similar findings for polyols [ Compernolle and Müller , ]. However, the timescales of convective updraft and other cloud dynamics (tens of minutes for systems with updraft velocities in the range of 10–40 m s −1 ) are of the same magnitude or smaller than those needed to achieve equilibrium at the clean conditions relevant for the Amazonian atmosphere.…”

Section: Model Descriptionmentioning

confidence: 99%

Organic aerosol processing in tropical deep convective clouds: Development of a new model (CRM‐ORG) and implications for sources of particle number

et al. 2015

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The difficulty in assessing interactions between atmospheric particles and clouds is due in part to the chemical complexity of the particles and to the wide range of length and timescales of processes occurring simultaneously during a cloud event. The new Cloud‐Resolving Model with Organics (CRM‐ORG) addresses these interactions by explicitly predicting the formation, transport, uptake, and re‐release of surrogate organic compounds consistent with the volatility basis set framework within a nonhydrostatic, three‐dimensional cloud‐resolving model. CRM‐ORG incorporates photochemical production, explicit condensation/evaporation of organic and inorganic vapors, and a comprehensive set of four different mechanisms describing particle formation from organic vapors and sulfuric acid. We simulate two deep convective cloud events over the Amazon rain forest in March 1998 and compare modeled particle size distributions with airborne observations made during the time period. The model predictions agree well with the observations for Aitken mode particles in the convective outflow (10–14 km) but underpredict nucleation mode particles by a factor of 20. A strong in‐cloud particle formation process from organic vapors alone is necessary to reproduce even relatively low ultrafine particle number concentrations (~1500 cm−3). Sensitivity tests with variable initial aerosol loading and initial vertical aerosol profile demonstrate the complexity of particle redistribution and net gain or loss in the cloud. In‐cloud particle number concentrations could be enhanced by as much as a factor of 3 over the base case simulation in the cloud outflow but were never reduced by more than a factor of 2 lower than the base. Additional sensitivity cases emphasize the need for constrained estimates of surface tension and affinity of organic vapors to ice surfaces. When temperature‐dependent organic surface tension is introduced to the new particle formation mechanisms, the number concentration of particles decreases by 60% in the cloud outflow. These uncertainties are discussed in light of the other prominent challenges for understanding the interactions between organic aerosols and clouds. Recommendations for future theoretical, laboratory, and field work are proposed.

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Henry's law constants of polyols

Cited by 15 publications

References 84 publications

Volatility dependence of Henry's law constants of condensable organics: Application to estimate depositional loss of secondary organic aerosols

Volatility dependence of Henry's law constants of condensable organics: Application to estimate depositional loss of secondary organic aerosols

Development of a protocol for the auto-generation of explicit aqueous-phase oxidation schemes of organic compounds

Organic aerosol processing in tropical deep convective clouds: Development of a new model (CRM‐ORG) and implications for sources of particle number

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