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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 29 (1998), S. 85-107 
    ISSN: 1573-0662
    Keywords: Henry's law ; solubility ; aerosol ; fluoroacetic acid ; chloroacetic acid ; bromoacetic acid ; difluoroacetic acid ; dichloroacetic acid ; dibromoacetic acid ; trifluoroacetic acid ; trichloroacetic acid ; tribromoacetic acid ; chloro-difluoroacetic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Henry's law constants K′H (mol kg-1 atm-1) have been measured between 278.15 K and 308.15 K for the following organic acids: CH2FCOOH (ln(K′H[298.15 K]) = 11.3 ± 0.2), CH2ClCOOH (11.59 ± 0.14), CH2BrCOOH (11.94 ± 0.21), CHF2COOH (10.32 ± 0.10), CHCl2COOH (11.69 ± 0.11), CHBr2COOH (12.33 ± 0.29), CBr3COOH (12.61 ± 0.21), and CClF2COOH (10.11 ± 0.12). The variation of K′H with temperature was determined for all acids except CH2FCOOH and CBr3COOH, with Δr H° for the dissolution reaction ranging from −85.2 ± 2.6 to −57.1 ± 2.5 kJ mol-1, meaning that their solubility is generally more sensitive to temperature than is the case for the simple carboxylic acids. The Henry's law constants show consistent trends with halogen substitution and, together with their high solubility compared to the parent (acetic) acid (ln(K′H[298.15 K]) = 8.61), present a severe test of current predictive models based upon molecular structure. The solubility of haloacetic acids and strong dissociation at normal pH mean that they will partition almost entirely into cloud and fog in the atmosphere (0.05–1.0 g H2O m-3), but can reside in both phases for the liquid water contents typical of aerosols (10-5-10-4 g H2O m-3).
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  • 2
    ISSN: 1573-0662
    Keywords: Henry's law ; solubility ; removal ; salt effect ; formic acid ; acetic acid ; propionic acid ; n-butyric acid ; isobutyric acid ; n-valeric acid ; isovaleric acid ; neovaleric acid ; n-caproic acid ; pyruvic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Henry's law constantsK′ H (mol kg−1 atm−1) have been determined at 298.15 K for the following organic acids: formic acid (5.53±0.27×103); acetic acid (5.50±0.29×103); propionic acid (5.71±0.34×103);n-butyric acid (4.73±0.18×103); isobutyric acid (1.13±0.12×103); isovaleric acid (1.20±0.11×103) and neovaleric acid (0.353±0.04×103). They have also been determined fromT=278.15 K toT=308.15 K forn-valeric acid (ln(K′ H)=−14.3371+6582.96/T);n-caproic acid (ln(K′ H)=−13.9424+6303.73/T) and pyruvic acid (ln(K′ H)=−4.41706+5087.92/T). The influence of 9 salts on the solubility of pyruvic acid at 298.15 K has been measured. Pyruvic acid is soluble enough to partition strongly into aqueous atmospheric aerosols. Other acids require around 1 g of liquid water m−3 (typical of clouds) to partition significantly into the aqueous phase. The degree of partitioning is sensitive to temperature. Considering solubility and dissociation (to formate) alone, the ratio of formic acid to acetic acid in liquid water in the atmosphere (at equilibrium with the gas phase acids) is expected to increase with rising pH, but show little variation with temperature.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Water, air & soil pollution 101 (1998), S. 197-215 
    ISSN: 1573-2932
    Keywords: Henry's law ; solubility ; trichloroacetic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The Henry's law constant of trichloroacetic acid [K′H (mol kg-1 atm-1) for the equilibrium CCl3COOH(g) ⇌ CCl3COOH(aq)] has been determined from measured partial pressures over aqueous solutions at 298.15 K and 308.15 K. Its value is given by: ln(K′H) = (11.21 ± 0.5) – 8.66 × 103 (l/Tr – l/T) where T (K) is temperature and Tr is equal to 298.15 K, for an aqueous phase dissociation constant (Ka) of 0.55 mol kg-1 determined from literature osmotic coefficient and electromotive force data. Accuracy is estimated to be 4–30% in the product K′HKa. Trichloroacetic acid is highly soluble and will partition strongly into aqueous atmospheric aerosols, and completely into fog and cloud water. Its occurrence and transport in the environment are therefore to be associated primarily with liquid phases.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 21 (1995), S. 81-95 
    ISSN: 1573-0662
    Keywords: Hypochlorous acid ; Henry's law ; stratospheric aerosol ; solubility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Henry's law constants K′H (mol kg−1 atm−1) for the reaction HOCl(g)=HOCl(aq) near room temperature, literature data for the associated enthalpy change, and solubilities of HOCl in aqueous H2SO4 (46 to 60 wt%) at temperatures relevant to the stratosphere (200 K≤T≤230 K) are shown to be thermodynamically consistent. Effective Henry's law constants [H*=mHOCl/pHOCl, in mol kg−1 atm−1] of HOCl in aqueous H2SO4 are given by: ln(H*)=6.4946−mH2SO4(−0.04107+54.56/T)−5862 (1/To−1/T) where T(K) is temperature and To=298.15K. The activity coefficient of HOCl in aqueous H2SO4 has a simple Setchenow-type dependence upon H2SO4 molality.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 7 (1988), S. 1-18 
    ISSN: 1573-0662
    Keywords: Hydrobromic acid ; hydrochloric acid ; hydrofluoric acid ; hydro-iodic acid ; nitric acid ; methanesulphonic acid ; solubility ; Henry's law ; seasalt ; aerosol ; degassing ; activity coefficient ; Pitzer model ; fluoride depletion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The following Henry's law constants (K H/mol2kg-2atm-1) for HNO3 and the hydrohalic acids have been evaluated from available partial pressure and other thermodynamic data from 0°–40°C, 1 atm total pressure: HNO 3 , 40°C–5.85×105; 30°C–1.50×106; 25°C–2.45×106; 20°C–4.04×106; 10°C–1.15×107; 0°C–3.41×107. HF, 40°C–3.2; 30°C–6.6; 25°C–9.61; 20°C–14.0; 10°C–32.0; 0°C–76. HCl, 40°C–4.66×105; 30°C–1.23×106; 25°C–2.04×106; 20°C–3.37×106; 10°C–9.71×106; 0°C–2.95×107. HBr, 40°C–2.5×108; 30°C–7.5×108; 25°C–1.32×109; 20°C–2.37×109; 10°C–8.10×109; 0°C–3.0×1010. HI, 40°C–5.2×108; 30°C–1.5×109; 25°C–2.5×109; 20°C–4.5×109; 10°C–1.5×1010; 0°C–5.0×1010. Simple equilibrium models suggest that HNO3, CH3SO3H and other acids up to 10x less soluble than HCl displace it from marine seasalt aerosols. HF is displaced preferentially to HCl by dissolved acidity at all relative humidities greater than about 80%, and should be entirely depleted in aged marine aerosols.
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