The dissociation constant and Henry's law constant of HCl in aqueous solution

Marsh, A. R. W.; McElroy, W.J.

doi:10.1016/0004-6981(85)90192-1

Cited by 97 publications

(32 citation statements)

References 11 publications

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“…Published constants for HCl vary over three orders of magnitude (see Sander, 1999). The value used for the calculations reported herein (1.1 M atm −1 , Marsh and McElroy, 1985) is similar to that reported by Brimblecombe and Clegg (1989) but is at the lower limit of published values. If the actual Henry's Law constant for HCl is greater, aerosol acidities must be proportionately greater to sustain the measured phase partitioning.…”

Section: Aerosol Aciditysupporting

confidence: 89%

“…was evaluated based on simultaneous measurements of HCl g (assumed equal to HCl * ) and particulate Cl − concentrations in air, the Henry's Law (K H ) and acid dissociation constants (K aHCl ) and associated temperature corrections for HCl (Marsh and McElroy, 1985), liquid water contents (LWCs) for sea-salt dominated size fractions calculated from hygroscopicity models (e.g. Gerber, 1985;Gong et al, 1997), and activity coefficients (Pitzer, 1991).…”

Section: Thermodynamic Calculationsmentioning

confidence: 99%

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Halogen cycling and aerosol pH in the Hawaiian marine boundary layer

Pszenny

Moldanová²,

Keene³

et al. 2004

Atmos. Chem. Phys.

135

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Abstract. Halogen species (HCl * (primarily HCl), Cl * (including Cl 2 and HOCl), BrO, total gaseous inorganic Br and size-resolved particulate Cl − and Br − ) and related chemical and physical parameters were measured in surface air at Oahu, Hawaii during September 1999. Aerosol pH as a function of particle size was inferred from phase partitioning and thermodynamic properties of HCl. Mixing ratios of halogen compounds and aerosol pHs were simulated with a new version of the photochemical box model MOCCA that considers multiple aerosol size bins.Inferred aerosol pHs ranged from 4.5 to 5.4 (median 5.1, n=22) for super-µm (primarily sea-salt) size fractions and 2.6 to 5.3 (median 4.6) for sub-µm (primarily sulphate) fractions. Inferred daytime pHs tended to be slightly lower than those at night, although daytime median values did not differ statistically from nighttime medians. Simulated pHs for most sea-salt size bins were within the range of inferred values. However, simulated pHs for the largest size fraction in the model were somewhat higher (oscillating around 5.9) due to the rapid turnover rates and relatively larger infusions of sea-salt alkalinity associated with fresh aerosols.Measured mixing ratios of HCl * ranged from <30 to 250 pmol mol −1 and those for Cl * from <6 to 38 pmol mol −1 .Simulated HCl and Cl * (Cl + ClO + HOCl + Cl 2 ) mixing ratios ranged between 20 and 70 pmol mol −1 and 0.5 and 6 pmol mol −1 , respectively. Afternoon HCl * maxima occurred on some days but consistent diel cycles for HCl * and Cl * were not observed. Simulated HCl did vary diurnally, peaking before dusk and reaching a minimum at dawn. While individual Correspondence to: A. A. P. Pszenny (alex.pszenny@unh.edu) components of Cl * varied diurnally in the simulations, their sum did not, consistent with the lack of a diel cycle in observed Cl * .Mixing ratios of total gaseous inorganic Br varied from <1.5 to 9 pmol mol −1 and particulate Br − deficits varied from 1 to 6 pmol mol −1 with values for both tending to be greater during daytime. Simulated Br t and Br − mixing ratios and enrichment factors (EFBr) were similar to those observed, with early morning maxima and dusk minima. However, the diel cycles differed in detail among the various simulations. In low-salt simulations, halogen cycling was less intense, Br − accumulated and Br t and EFBr increased slowly overnight. In higher-salt simulations with more intense halogen cycling, Br − and EFBr decreased and Br t increased rapidly after dusk. Cloud processing, which is not considered in this version of MOCCA, may also affect these diel cycles (von Glasow et al., 2003). Measured BrO was never above detection limit (≈2 pmol mol −1 ) during the experiment, however relative changes in the BrO signal during the 3-hour period ending at 11:00 local time were mostly negative, averaging −0.3 pmol mol −1 . Both of these results are consistent with MOCCA simulations of BrO mixing ratios.Increasing the sea-salt mixing ratio in MOCCA by ≈25% (within observed range) led to a decrease i...

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Section: Aerosol Aciditysupporting

confidence: 89%

Section: Thermodynamic Calculationsmentioning

confidence: 99%

Halogen cycling and aerosol pH in the Hawaiian marine boundary layer

Pszenny

Moldanová²,

Keene³

et al. 2004

Atmos. Chem. Phys.

135

View full text Add to dashboard Cite

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“…The diabatic freezing time is determined by the rate of latent heat removal to the underlying rime substrate Inter-and extrapolated from Brownscombe and Hallett (1967); Macklin andPayne (1967, 1969). 2 Calculated for the corresponding LWCs for 3m s −1 (Macklin and Payne, 1967 Calculated at 0 • C and at the corresponding pH (Warneck and Williams, 2012;Barret et al, 2011;Johnson et al, 1996;Compernolle and Müller, 2014;Marsh and McElroy, 1985;Schwartz and White, 1981;Hales and Drewes, 1979;Maahs, 1982). 5 The mass accommodation coefficients (α at 273K) are taken from a review paper (Davidovits et al, 2006) or estimated as described elsewhere (Ervens et al, 2003).…”

Section: Model Descriptionmentioning

confidence: 99%

Chemistry of riming: the retention of organic and inorganic atmospheric trace constituents

Jost

Szakáll²,

Diehl³

et al. 2017

Atmos. Chem. Phys.

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Abstract. During free fall in clouds, ice hydrometeors such as snowflakes and ice particles grow effectively by riming, i.e., the accretion of supercooled droplets. Volatile atmospheric trace constituents dissolved in the supercooled droplets may remain in ice during freezing or may be released back to the gas phase. This process is quantified by retention coefficients. Once in the ice phase the trace constituents may be vertically redistributed by scavenging and subsequent precipitation or by evaporation of these ice hydrometeors at high altitudes. Retention coefficients of the most dominant carboxylic acids and aldehydes found in cloud water were investigated in the Mainz vertical wind tunnel under dry-growth (surface temperature less than 0 • C) riming conditions which are typically prevailing in the mixed-phase zone of convective clouds (i.e., temperatures from −16 to −7 • C and a liquid water content (LWC) of 0.9±0.2 g m −3 ). The mean retention coefficients of formic and acetic acids are found to be 0.68 ± 0.09 and 0.63 ± 0.19. Oxalic and malonic acids as well as formaldehyde show mean retention coefficients of 0.97 ± 0.06, 0.98 ± 0.08, and 0.97 ± 0.11, respectively. Application of a semi-empirical model on the present and earlier wind tunnel measurements reveals that retention coefficients can be well interpreted by the effective Henry's law constant accounting for solubility and dissociation. A parameterization for the retention coefficients has been derived for substances whose aqueous-phase kinetics are fast compared to mass transport timescales. For other cases, the semi-empirical model in combination with a kinetic approach is suited to determine the retention coefficients. These may be implemented in high-resolution cloud models.

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“…We measured volatile inorganic CI gases in parallel at the same location using the tandem-mist-chamber technique Assuming the density of sea salt equals that of NaCl (2.165 g cm '3) and a Na/sea-salt mass ratio of 0.3076 [Wilson, 1975], the Na mass per dry particle (N%•, g particle 'l) is given by [Marsh and McElroy, 1985], the pH of an aerosol droplet required to sustain the measured CI phase partitioning at equilibrium can be calculated directly. Since this approach requires that the sea-salt aerosol be completely deliquesced, we restrict the analysis to samples collected at RHs greater than 75%, the approximate deliquescence point for NaCI [Tang, 1997] …”

Section: Introductionmentioning

confidence: 99%

The pH of deliquesced sea‐salt aerosol in polluted marine air

Keene

Savoie

1998

Geophysical Research Letters

117

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Abstract. The pH of deliquesced sea-salt aerosol was derived from the Cl phase partitioning measured in marine air, corresponding meteorological conditions, and the thermodynamic properties of HCI. Under moderately polluted conditions at Bermuda during spring 1996, calculated sea-salt aerosol pH ranged from the mid-2s to the mid-3s. Cl' and NO3' concentrations in the lower half of the sea-salt size distribution were near thermodynamic equilibrium with respect to HCIg and HNO3g; shorter aerosol lifetimes and slower reaction kinetics involving larger aerosol sustained moderate phase disequilibria. The active multiphase cycling of HCI buffered sea-salt aerosol pH to approximately the same value across the particle size spectrum.

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The dissociation constant and Henry's law constant of HCl in aqueous solution

Cited by 97 publications

References 11 publications

Halogen cycling and aerosol pH in the Hawaiian marine boundary layer

Halogen cycling and aerosol pH in the Hawaiian marine boundary layer

Chemistry of riming: the retention of organic and inorganic atmospheric trace constituents

The pH of deliquesced sea‐salt aerosol in polluted marine air

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